WO2013077271A1 - Adhesive composition, adhesive layer, polarizing film having adhesive layer, and image formation device - Google Patents
Adhesive composition, adhesive layer, polarizing film having adhesive layer, and image formation device Download PDFInfo
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- WO2013077271A1 WO2013077271A1 PCT/JP2012/079819 JP2012079819W WO2013077271A1 WO 2013077271 A1 WO2013077271 A1 WO 2013077271A1 JP 2012079819 W JP2012079819 W JP 2012079819W WO 2013077271 A1 WO2013077271 A1 WO 2013077271A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2170/00—Compositions for adhesives
- C08G2170/40—Compositions for pressure-sensitive adhesives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
- C09K2323/05—Bonding or intermediate layer characterised by chemical composition, e.g. sealant or spacer
- C09K2323/059—Unsaturated aliphatic polymer, e.g. vinyl
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/266—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension of base or substrate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2843—Web or sheet containing structurally defined element or component and having an adhesive outermost layer including a primer layer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2848—Three or more layers
Definitions
- the present invention relates to a pressure-sensitive adhesive composition having an excellent antistatic function, a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition, a polarizing film, and a polarizing film with a pressure-sensitive adhesive layer having the pressure-sensitive adhesive layer. Furthermore, the present invention relates to an image display device such as a liquid crystal display device, an organic EL display device, or a PDP using the polarizing film with an adhesive layer.
- polarizing plates (hereinafter, “polarizing plates” are also referred to as “polarizing films”) are used. It is stuck. When sticking the said polarizing film to a liquid crystal cell, an adhesive is normally used. Moreover, since adhesion
- the pressure-sensitive adhesive has a pressure-sensitive adhesive layer provided in advance as a pressure-sensitive adhesive layer on one side of the polarizing film because it has a merit that a drying step is not required to fix the polarizing film.
- a film is generally used.
- a release film is usually attached to the pressure-sensitive adhesive layer of the polarizing film with a pressure-sensitive adhesive layer.
- the release film is peeled off from the pressure-sensitive adhesive layer of the polarizing film with the pressure-sensitive adhesive layer. Static electricity is generated.
- the static electricity generated in this way affects the orientation of the liquid crystal inside the liquid crystal display device, leading to defects. Further, display unevenness due to static electricity may occur when the liquid crystal display device is used.
- the generation of static electricity can be suppressed, for example, by forming an antistatic layer on the outer surface of the polarizing film, but the effect is small and there is a problem that static electricity generation cannot be fundamentally prevented.
- Patent Documents 1 to 6 As a means for imparting an antistatic function to the pressure-sensitive adhesive layer, for example, blending an ionic compound with the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer has been proposed (Patent Documents 1 to 6).
- JP 2005-306937 A JP-T 2006-1111846 JP 2008-517138 A Special table 2010-523806 JP 2011-016990 A JP2011-017000A
- an antistatic function of the pressure-sensitive adhesive layer is imparted by adding an ionic compound having a bis (pentafluoroethanesulfonyl) imide anion as an anionic component to the pressure-sensitive adhesive composition.
- an antistatic function of the pressure-sensitive adhesive layer is achieved by adding an ionic compound having a bistrifluoromethanesulfonimide anion or a bistrifluoroethanesulfonimide anion as an anion component to the pressure-sensitive adhesive composition. Has been granted.
- the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition containing these ionic compounds is exposed to conditions of room temperature and normal humidity or higher, such as wet heat conditions such as 60 ° C., 90% RH, 60 ° C., and 95% RH. If this is done, the surface resistance value may increase and the antistatic function may be impaired.
- Patent Documents 5 and 6 when an ionic compound having an imide anion containing a perfluoroalkyl group having a carbon atom is added to the pressure-sensitive adhesive composition, the antistatic function of the pressure-sensitive adhesive layer is not sufficiently improved. It describes that the antistatic function of the adhesive layer can be improved when an ionic compound having a bis (fluorosulfonyl) imide anion is added to the adhesive composition.
- the inventions described in these patent documents are not intended to suppress an increase in the surface resistance value after the humidification test, and therefore specific description of the surface resistance value when exposed to wet heat conditions. There is no suggestion.
- the present invention provides a pressure-sensitive adhesive composition, a pressure-sensitive adhesive layer, and a polarizing film with a pressure-sensitive adhesive layer that can form a pressure-sensitive adhesive layer that is excellent in main characteristics such as durability and that is particularly excellent in humidification durability of an antistatic function. With the goal.
- Another object of the present invention is to provide an image display device using the polarizing film with the pressure-sensitive adhesive layer.
- the present invention is a pressure-sensitive adhesive composition containing a (meth) acrylic polymer (A) and an ionic compound (B) having an anionic component and a cationic component, and the (meth) acrylic polymer (A) Is an aromatic ring-containing (meth) acrylic polymer (A) containing an aromatic ring-containing alkyl (meth) acrylate as a monomer unit.
- the anion component is preferably an anion component having an organic group and having 2 or more carbon atoms.
- the anion component is represented by the following general formula (1): (C n F 2n + 1 SO 2 ) 2 N ⁇ (1) (In the general formula (1), n is an integer of 1 to 10), the following general formula (2): CF 2 (C m F 2m SO 2 ) 2 N ⁇ (2) (In the general formula (2), m is an integer of 2 to 10): and the following general formula (3): - O 3 S (CF 2) l SO 3 - (3) It is preferable that at least one anion component represented by (in general formula (3), l is an integer of 3 to 10).
- the cation component of the ionic compound (B) is preferably at least one of an alkali metal cation and an organic cation, and the cation component of the ionic compound (B) is lithium. More preferably, it is a cation.
- the cation component of the ionic compound (B) is preferably an organic cation having 4 to 10 carbon atoms.
- the anionic component of the ionic compound (B) is bis (trifluoromethanesulfonyl) imide anion, bis (heptafluoropropanesulfonyl) imide anion, bis (nonafluorobutanesulfonyl) imide anion, cyclo It is preferably at least one of hexafluoropropane-1,3-bis (sulfonyl) imide anion and hexafluoropropane-1,3-disulfonic acid anion.
- 0.001 to 10 parts by weight of the ionic compound (B) is preferably contained with respect to 100 parts by weight of the aromatic ring-containing (meth) acrylic polymer (A).
- the aromatic ring-containing alkyl (meth) acrylate contains at least one of benzyl (meth) acrylate and phenoxyethyl (meth) acrylate.
- the aromatic ring-containing (meth) acrylic polymer (A) further contains a hydroxyl group-containing monomer as a monomer unit. Furthermore, it is preferable that the aromatic ring-containing (meth) acrylic polymer (A) further contains a carboxyl group-containing monomer as a monomer unit.
- the said adhesive composition it is preferable to contain a crosslinking agent (C) further, and the said crosslinking agent (C) is 0 with respect to 100 weight part of said aromatic ring containing (meth) acrylic-type polymers (A). More preferably, the content is 0.01 to 20 parts by weight, and the crosslinking agent (C) is more preferably at least one of an isocyanate compound and a peroxide.
- the aromatic ring-containing (meth) acrylic polymer (A) preferably has a weight average molecular weight of 500,000 to 3,000,000.
- the present invention relates to a pressure-sensitive adhesive layer characterized by being formed from any one of the pressure-sensitive adhesive compositions described above.
- the present invention also relates to a polarizing film with a pressure-sensitive adhesive layer comprising at least a polarizing film having a transparent protective film on one or both sides of a polarizer and the pressure-sensitive adhesive layer described above.
- the transparent protective film is preferably a triacetyl cellulose film, a (meth) acrylic resin film, or a cyclic polyolefin polymer film.
- the thickness of the polarizer is preferably 1 to 10 ⁇ m.
- the present invention relates to an image display device using at least one polarizing film with an adhesive layer described above.
- an antistatic function can be imparted by blending an ionic compound with the adhesive.
- an ionic compound is present on the surface of the pressure-sensitive adhesive layer, the adhesive force between the pressure-sensitive adhesive layer and the adherend may be reduced, and when exposed to wet heat conditions, the surface resistance value after the test is The antistatic function may be impaired.
- the pressure-sensitive adhesive composition according to the present invention contains an ionic compound (B) that can provide an antistatic function in addition to the (meth) acrylic polymer (A) that is a base polymer.
- the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition has an excellent antistatic function.
- the pressure-sensitive adhesive composition according to the present invention includes an ionic compound (B) having an organic group and an anionic component having 2 or more carbon atoms, particularly an ionic compound (B) having a relatively large molecular weight of the anionic component. ) Or an ionic compound (B) having an anionic component having a cyclic structure, the surface resistance value of the pressure-sensitive adhesive layer can be kept low even after the humidification test.
- the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to the present invention and the pressure-sensitive adhesive layer-attached polarizing film having the pressure-sensitive adhesive layer are excellent in main characteristics such as durability, and at the same time, in particular, humidification durability with an antistatic function Excellent in properties.
- the aromatic ring-containing (meth) acrylic polymer (A) is used as the (meth) acrylic polymer (A), unevenness after heating is prevented, and various physical properties such as durability are well balanced. improves.
- various physical properties such as durability are improved in a particularly balanced manner. .
- the pressure-sensitive adhesive composition according to the present invention contains an aromatic ring-containing (meth) acrylic polymer (A) as a base polymer.
- the aromatic ring-containing (meth) acrylic polymer (A) usually contains alkyl (meth) acrylate as a main component as a monomer unit.
- (Meth) acrylate refers to acrylate and / or methacrylate, and (meth) of the present invention has the same meaning.
- alkyl (meth) acrylate constituting the main skeleton of the aromatic ring-containing (meth) acrylic polymer (A) include linear or branched alkyl groups having 1 to 18 carbon atoms.
- the alkyl group includes methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, amyl group, hexyl group, cyclohexyl group, heptyl group, 2-ethylhexyl group, isooctyl group, nonyl group, decyl group.
- alkyl groups preferably have an average carbon number of 3 to 9.
- the aromatic ring-containing (meth) acrylic polymer (A) contains phenoxyethyl (meth) acrylate
- An aromatic ring-containing alkyl (meth) acrylate such as benzyl (meth) acrylate is used.
- the aromatic ring-containing alkyl (meth) acrylate can be used by mixing a polymer obtained by polymerizing the aromatic ring-containing alkyl (meth) acrylate with the exemplified (meth) acrylic polymer.
- the alkyl (meth) acrylate containing an aromatic ring The (meth) acrylate is preferably used after being copolymerized with the alkyl (meth) acrylate.
- the ratio of the aromatic ring-containing alkyl (meth) acrylate in the aromatic ring-containing (meth) acrylic polymer (A) is preferably 5 to 30% by weight in the weight ratio of all constituent monomers (100% by weight), Is preferably 10 to 25% by weight.
- a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group for the purpose of improving adhesiveness and heat resistance.
- One or more copolymerizable monomers having a group can be introduced by copolymerization.
- Such copolymerizable monomers include, for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) acrylic acid 6 Hydroxyl-containing monomers such as hydroxyhexyl, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate and (4-hydroxymethylcyclohexyl) -methyl acrylate Carboxyl group-containing monomers such as (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid and crotonic acid; acid anhydrides such as maleic anhydride and itaconic anhydride Substance-based material -Caprolactone adduct of acrylic acid; styrene sulf
- (N-substituted) amides such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide, etc.
- Further modifying monomers include vinyl acetate, vinyl propionate, N-vinyl pyrrolidone, methyl vinyl pyrrolidone, vinyl pyridine, vinyl piperidone, vinyl pyrimidine, vinyl piperazine, vinyl pyrazine, vinyl pyrrole, vinyl imidazole, vinyl oxazole, vinyl morpholine, N- Vinyl monomers such as vinylcarboxylic amides, styrene, ⁇ -methylstyrene, N-vinylcaprolactam; cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; epoxy group-containing acrylic monomers such as glycidyl (meth) acrylate; (Meth) acrylic acid polyethylene glycol, (meth) acrylic acid polypropylene glycol, (meth) acrylic acid methoxyethylene glycol, (meth) acrylic acid meso Glycol acrylic ester monomers such as xypolypropylene glycol; acrylic ester monomers such as
- examples of copolymerizable monomers other than the above include silane-based monomers containing silicon atoms.
- examples of the silane monomer include 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, and 8-vinyloctyltrimethoxysilane.
- copolymer monomers examples include tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neo Pentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate (Meth) acrylic acid such as esterified product of (meth) acrylic acid and polyhydric alcohol such as caprolactone-modified dipentaerythritol hexa (meth) acrylate Polyfunctional monomers having two or more uns
- Polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate and the like to which two or more unsaturated double bonds are added can also be used.
- the aromatic ring-containing (meth) acrylic polymer (A) is based on the alkyl (meth) acrylate as a main component in the weight ratio of all the constituent monomers, and the above-mentioned copolymer in the aromatic ring-containing (meth) acrylic polymer (A).
- the ratio of the polymerization monomer is not particularly limited, but the ratio of the copolymerization monomer is about 0 to 20%, about 0.1 to 15%, and further about 0.1 to 10% in the weight ratio of all the constituent monomers. Is preferred.
- hydroxyl group-containing monomers and carboxyl group-containing monomers are preferably used from the viewpoint of adhesion and durability.
- a hydroxyl group-containing monomer and a carboxyl group-containing monomer can be used in combination.
- These copolymerization monomers serve as reaction points with the crosslinking agent when the pressure-sensitive adhesive composition contains a crosslinking agent. Since a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and the like are rich in reactivity with an intermolecular crosslinking agent, they are preferably used for improving the cohesiveness and heat resistance of the resulting pressure-sensitive adhesive layer.
- a hydroxyl group-containing monomer is preferable from the viewpoint of reworkability, and a carboxyl group-containing monomer is preferable from the viewpoint of achieving both durability and reworkability.
- the proportion is preferably 0.01 to 15% by weight, more preferably 0.03 to 10% by weight, and further preferably 0.05 to 7% by weight.
- the proportion is preferably 0.05 to 10% by weight, more preferably 0.1 to 8% by weight, and further preferably 0.2 to 6% by weight. .
- the aromatic ring-containing (meth) acrylic polymer (A) of the present invention those having a weight average molecular weight in the range of 500,000 to 3,000,000 are usually used. In view of durability, particularly heat resistance, it is preferable to use those having a weight average molecular weight of 700,000 to 2,700,000. Further, it is preferably 800,000 to 2.5 million. A weight average molecular weight of less than 500,000 is not preferable in terms of heat resistance. On the other hand, if the weight average molecular weight is more than 3 million, a large amount of dilution solvent is required to adjust the viscosity for coating, which is not preferable.
- the weight average molecular weight is a value measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene.
- aromatic ring-containing (meth) acrylic polymer (A) can be appropriately selected from known production methods such as solution polymerization, bulk polymerization, emulsion polymerization, and various radical polymerizations.
- the obtained aromatic ring-containing (meth) acrylic polymer (A) may be a random copolymer, a block copolymer, a graft copolymer or the like.
- solution polymerization for example, ethyl acetate, toluene or the like is used as a polymerization solvent.
- the reaction is carried out under an inert gas stream such as nitrogen and a polymerization initiator is added, usually at about 50 to 70 ° C. under reaction conditions for about 5 to 30 hours.
- the polymerization initiator, chain transfer agent, emulsifier and the like used for radical polymerization are not particularly limited and can be appropriately selected and used.
- the weight average molecular weight of the aromatic ring-containing (meth) acrylic polymer (A) can be controlled by the amount of polymerization initiator, the amount of chain transfer agent used, and the reaction conditions. The amount is adjusted.
- polymerization initiator examples include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (5-methyl-2 -Imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) disulfate, 2,2'-azobis (N, N'-dimethyleneisobutylamidine), 2,2 Azo initiators such as' -azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (VA-057, manufactured by Wako Pure Chemical Industries, Ltd.), persulfates such as potassium persulfate and ammonium persulfate , Di (2-ethylhexyl) peroxydicarbonate, di (4-tert-butylcyclohexyl) peroxydicarbonate, di-sec-butyl Peroxydicarbonate, t
- the polymerization initiator may be used singly or as a mixture of two or more, but the total content is 0.005 to 1 part by weight with respect to 100 parts by weight of the monomer. Is preferably about 0.02 to 0.5 parts by weight.
- the aromatic ring-containing (meth) acrylic polymer (A) having a weight average molecular weight by using, for example, 2,2′-azobisisobutyronitrile as a polymerization initiator, polymerization is started.
- the amount of the agent used is preferably about 0.06 to 0.2 parts by weight, more preferably about 0.08 to 0.175 parts by weight, based on 100 parts by weight of the total amount of monomer components. .
- chain transfer agent examples include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, and 2,3-dimercapto-1-propanol.
- the chain transfer agent may be used alone or in combination of two or more, but the total content is 0.1 parts by weight with respect to 100 parts by weight of the total amount of monomer components. Less than or equal to
- emulsifier used in emulsion polymerization examples include anionic emulsifiers such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, ammonium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate, and polyoxy Nonionic emulsifiers such as ethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene-polyoxypropylene block polymer and the like can be mentioned. These emulsifiers may be used alone or in combination of two or more.
- reactive emulsifiers emulsifiers into which radical polymerizable functional groups such as propenyl groups and allyl ether groups are introduced, specifically, for example, Aqualon HS-10, HS-20, KH-10, BC-05 BC-10, BC-20 (all of which are manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adekaria soap SE10N (manufactured by Asahi Denka Kogyo Co., Ltd.), and the like.
- Reactive emulsifiers are preferable because they are incorporated into the polymer chain after polymerization and thus have improved water resistance.
- the amount of the emulsifier used is preferably 0.3 to 5 parts by weight with respect to 100 parts by weight of the total amount of monomer components, and more preferably 0.5 to 1 part by weight from the viewpoint of polymerization stability and mechanical stability.
- the pressure-sensitive adhesive composition according to the present invention contains an ionic compound (B) in addition to the aromatic ring-containing (meth) acrylic polymer (A), and the ionic compound (B) contains an anionic component and Has a cationic component.
- the anion component is represented by the following general formula (1): (C n F 2n + 1 SO 2 ) 2 N ⁇ (1) (In the general formula (1), n is an integer of 1 to 10), the following general formula (2): CF 2 (C m F 2m SO 2 ) 2 N ⁇ (2) (In the general formula (2), m is an integer of 2 to 10): and the following general formula (3): - O 3 S (CF 2) l SO 3 - (3) (In general formula (3), l is an integer of 3 to 10), and when used together with the aromatic ring-containing (meth) acrylic polymer (A), It is preferable because an antistatic function can be imparted while significantly lowering the durability as an agent.
- the anion component represented by the general formula (1) include bis (trifluoromethanesulfonyl) imide anion, bis (heptafluoropropanesulfonyl) imide anion, bis (nonafluorobutanesulfonyl) imide anion, bis (Undecafluoropentanesulfonyl) imide anion, bis (tridecafluorohexanesulfonyl) imide anion, bis (pentadecafluoroheptanesulfonyl) imide anion, and the like.
- bis (heptafluoropropanesulfonyl) imide anion or bis (nonafluorobutanesulfonyl) imide anion is particularly preferable.
- anion component represented by the general formula (2) examples include cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide anion, which can be preferably used.
- anion component represented by the general formula (3) examples include hexafluoropropane-1,3-disulfonic acid anion, which can be preferably used.
- the anionic component of the ionic compound (B) is preferably an anionic component having an organic group and having 2 or more carbon atoms.
- the pressure-sensitive adhesive composition according to the present invention contains an ionic compound (B) having a relatively large molecular weight of an anionic component or an ionic compound (B) having an anionic component having a cyclic structure, the pressure-sensitive adhesive composition may be subjected to a humidification test. However, the surface resistance value of the pressure-sensitive adhesive layer can be kept lower.
- cation component of ionic compound (B) examples include lithium, sodium, and potassium alkali metal ions, and together with the anion component, constitute an alkali metal salt as the ionic compound (B).
- the alkali metal ions in the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition containing the ionic compound (B) having potassium ions, the initial surface resistance value tends to increase.
- the ionic compound (B) having lithium ions is contained, an increase in the initial surface resistance value of the pressure-sensitive adhesive layer and the surface resistance value after humidification can be suppressed.
- the ionic compound (B) having lithium ions is preferable.
- alkali metal salt examples include bis (heptafluoropropanesulfonyl) imide lithium, bis (heptafluoropropanesulfonyl) imide sodium, bis (heptafluoropropanesulfonyl) imide potassium, and bis (nonafluorobutanesulfonyl) imide lithium.
- bis (heptafluoropropanesulfonyl) imide lithium bis (nonafluorobutanesulfonyl) imide lithium, cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide lithium, 1,1,2,2,3 2,3-hexafluoropropane-1,3-disulfonic acid dilithium salt is particularly preferred.
- examples of the cation component of the ionic compound (B) include an organic cation, and together with the anion component, constitutes an organic cation-anion salt as the ionic compound (B).
- Organic cation-anion salt is also called an ionic liquid or ionic solid.
- organic cation examples include a pyridinium cation, a piperidinium cation, a pyrrolidinium cation, a cation having a pyrroline skeleton, a cation having a pyrrole skeleton, an imidazolium cation, a tetrahydropyrimidinium cation, and a dihydropyrimidinium cation.
- organic cation having 4 to 10 carbon atoms is particularly preferable.
- organic cations a piperidinium cation is preferable, and an ethylmethylpyrrolidinium cation is particularly preferable.
- a compound comprising a combination of the above cation component and anion component is appropriately selected and used.
- 1-butyl-3-methylpyridinium bis (heptafluoropropanesulfonyl) imide 1-butyl-3-methylpyridinium bis (nonafluorobutanesulfonyl) imide, 1-butyl-3-methylpyridinium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide, bis (1-butyl-3-methyl Pyridinium) hexafluoropropane-1,3-disulfonic acid
- 1-ethyl-3-methylimidazolium bis (heptafluoropropanesulfonyl) imidoimide 1-ethyl-3-methylimidazolium bis (nonafluorobutanesulfonyl) imide, -Ethyl-3 Me
- ionic compound (B) in addition to the combination of the anion component and the cation component, alkali metal salts and organic cation-anion salts having the following combinations are also used as the ionic compound (B). Is possible.
- the alkali metal salt which has each ion of lithium, sodium, and potassium as a cation component, and the anion component shown below.
- the anion component include CH 3 COO ⁇ , CF 3 COO ⁇ , CH 3 SO 3 ⁇ , CF 3 SO 3 ⁇ , (CF 3 SO 2 ) 2 N ⁇ , (CF 3 SO 2 ) 3 C ⁇ , C 4 F 9 SO 3 -, (C 2 F 5 SO 2) 2 N -, C 3 F 7 COO -, (CF 3 SO 2) (CF 3 CO) N -, - O 3 S (CF 2) 3 SO 3 - , PF 6 ⁇ , CO 3 2 ⁇ , etc .; Cl ⁇ , Br ⁇ , I ⁇ , AlCl 4 ⁇ , Al 2 Cl 7 ⁇ , BF 4 ⁇ , PF 6 ⁇ , ClO 4 ⁇ , NO 3 ⁇ , AsF Examples thereof include inorganic substances such as 6 ⁇ , Sb
- an anion portion containing a fluorine atom is particularly preferable because an ionic compound having a good ion dissociation property is obtained.
- (CF 3 SO 2 ) 2 N ⁇ , (C 2 F 5 SO 2 ) 2 N (Perfluoroalkylsulfonyl) imide such as — is more preferable, and (trifluoromethanesulfonyl) imide represented by (CF 3 SO 2 ) 2 N ⁇ is more preferable.
- alkali metal organic salt examples include sodium acetate, sodium alginate, sodium lignin sulfonate, sodium toluenesulfonate, LiCF 3 SO 3 , Li (CF 3 SO 2 ) 2 N, Li (CF 3 SO 2 ) 2 N, Li (C 2 F 5 SO 2 ) 2 N, Li (C 2 F 5 SO 2 ) 2 N, Li (CF 3 SO 2 ) 3 C, KO 3 S (CF 2 ) 3 SO 3 K, LiO 3 S (CF 2) 3 SO 3 K , and the like, among these LiCF 3 SO 3, Li (CF 3 SO 2) 2 N, Li (CF 3 SO 2) iN, Li (C 2 F 5 SO 2 ) 2 N, Li (C 2 F 5 SO 2 ) 2 N, Li (CF 3 SO 2 ) 3 C and the like are preferable, and Li (CF 3 SO 2 ) 2 N, Li (CF 3 SO 2 ) IN, Li ( Fluorine-containing lithium imide salts such as C 2 F 5 SO 2 )
- An organic cation-anion salt composed of a cation component and an anion component.
- the cationic component is made of an organic substance.
- the cation component specifically, pyridinium cation, piperidinium cation, pyrrolidinium cation, cation having pyrroline skeleton, cation having pyrrole skeleton, imidazolium cation, tetrahydropyrimidinium cation, dihydropyrimidinium cation, Examples thereof include a pyrazolium cation, a pyrazolinium cation, a tetraalkylammonium cation, a trialkylsulfonium cation, and a tetraalkylphosphonium cation.
- anion component examples include Cl ⁇ , Br ⁇ , I ⁇ , AlCl 4 ⁇ , Al 2 Cl 7 ⁇ , BF 4 ⁇ , PF 6 ⁇ , ClO 4 ⁇ , NO 3 ⁇ , CH 3 COO ⁇ , CF 3.
- organic cation-anion salt a compound comprising a combination of the above cation component and anion component is appropriately selected and used.
- a compound comprising a combination of the above cation component and anion component is appropriately selected and used.
- the proportion of the ionic compound (B) in the pressure-sensitive adhesive composition of the present invention is preferably 0.001 to 10 parts by weight with respect to 100 parts by weight of the aromatic ring-containing (meth) acrylic polymer (A). If the said compound (B) is less than 0.001 weight part, the improvement effect of antistatic performance may not be enough.
- the compound (B) is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more. On the other hand, if the ionic compound (B) is more than 10 parts by weight, the durability may not be sufficient.
- the compound (B) is preferably 5 parts by weight or less, and more preferably 3 parts by weight or less.
- the ratio of the said compound (B) can employ
- the pressure-sensitive adhesive composition of the present invention can contain a crosslinking agent (C).
- a crosslinking agent C
- an organic crosslinking agent or a polyfunctional metal chelate can be used as the crosslinking agent (C).
- the organic crosslinking agent include an isocyanate crosslinking agent, a peroxide crosslinking agent, an epoxy crosslinking agent, and an imine crosslinking agent.
- a polyfunctional metal chelate is one in which a polyvalent metal is covalently or coordinately bonded to an organic compound.
- the polyvalent metal atom include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, and Ti. Can be mentioned.
- Examples of the atom in the organic compound that is covalently or coordinately bonded include an oxygen atom, and examples of the organic compound include an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, and a ketone compound.
- an isocyanate-based crosslinking agent and / or a peroxide-type crosslinking agent is preferable.
- the compound relating to the isocyanate-based crosslinking agent include isocyanate monomers such as tolylene diisocyanate, chlorophenylene diisocyanate, tetramethylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, and these isocyanate monomers.
- Examples include isocyanate compounds added with trimethylolpropane, isocyanurates, burette compounds, and urethane prepolymer isocyanates such as polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, and polyisoprene polyols. be able to.
- a polyisocyanate compound which is one or a polyisocyanate compound derived from one selected from the group consisting of hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate.
- hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, polyol-modified is selected from the group consisting of hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate or a polyisocyanate compound derived therefrom.
- examples include hexamethylene diisocyanate, polyol-modified hydrogenated xylylene diisocyanate, trimer-type hydrogenated xylylene diisocyanate, and polyol-modified isophorone diisocyanate.
- the exemplified polyisocyanate compound is preferable because the reaction with a hydroxyl group proceeds rapidly, particularly using an acid or base contained in the polymer as a catalyst, and thus contributes to the speed of crosslinking.
- any radical active species can be used as long as it generates radical active species by heating or light irradiation to advance the crosslinking of the base polymer of the pressure-sensitive adhesive composition.
- peroxides examples include di (2-ethylhexyl) peroxydicarbonate (1 minute half-life temperature: 90.6 ° C.), di (4-t-butylcyclohexyl) peroxydicarbonate (1 Minute half-life temperature: 92.1 ° C.), di-sec-butyl peroxydicarbonate (1 minute half-life temperature: 92.4 ° C.), t-butyl peroxyneodecanoate (1 minute half-life temperature: 103 0.5 ° C.), t-hexyl peroxypivalate (1 minute half-life temperature: 109.1 ° C.), t-butyl peroxypivalate (1 minute half-life temperature: 110.3 ° C.), dilauroyl peroxide ( 1 minute half-life temperature: 116.4 ° C.), di-n-octanoyl peroxide (1 minute half-life temperature: 117.4 ° C.), 1,1,3,3-tetramethylbutyl
- di (4-t-butylcyclohexyl) peroxydicarbonate (1 minute half-life temperature: 92.1 ° C.)
- dilauroyl peroxide (1 minute half-life temperature: 116. 4 ° C)
- dibenzoyl peroxide (1 minute half-life temperature: 130.0 ° C) and the like are preferably used.
- the peroxide half-life is an index representing the decomposition rate of the peroxide, and means the time until the remaining amount of peroxide is reduced to half.
- the decomposition temperature for obtaining a half-life at an arbitrary time and the half-life time at an arbitrary temperature are described in the manufacturer catalog, for example, “Organic peroxide catalog 9th edition by Nippon Oil & Fats Co., Ltd.” (May 2003) ".
- the amount of the crosslinking agent (C) used is preferably 0.01 to 20 parts by weight, more preferably 0.03 to 10 parts by weight, per 100 parts by weight of the aromatic ring-containing (meth) acrylic polymer (A). preferable. If the crosslinking agent (C) is less than 0.01 parts by weight, the cohesive force of the pressure-sensitive adhesive tends to be insufficient, and foaming may occur during heating. On the other hand, if it exceeds 20 parts by weight, the moisture resistance is sufficient. Instead, peeling is likely to occur in a reliability test.
- the isocyanate-based crosslinking agent may be used alone or in combination of two or more, but the total content is the aromatic ring-containing (meth) acrylic polymer.
- the polyisocyanate compound crosslinking agent is preferably 0.01 to 2 parts by weight, more preferably 0.02 to 2 parts by weight, more preferably 0.05 to 1.5 parts by weight based on 100 parts by weight. More preferably, it is part by weight. It can be appropriately contained in consideration of cohesive force and prevention of peeling in a durability test.
- the peroxide may be used alone or as a mixture of two or more, but the total content of the peroxide is the aromatic ring-containing (meth) acrylic polymer ( A)
- the peroxide is 0.01 to 2 parts by weight, preferably 0.04 to 1.5 parts by weight, more preferably 0.05 to 1 part by weight with respect to 100 parts by weight. . In order to adjust processability, reworkability, cross-linking stability, peelability, and the like, it is appropriately selected within this range.
- the peroxide decomposition amount remaining after the reaction treatment for example, it can be measured by HPLC (High Performance Liquid Chromatography).
- the pressure-sensitive adhesive composition after the reaction treatment is taken out, immersed in 10 ml of ethyl acetate, extracted by shaking at 25 ° C. and 120 rpm for 3 hours with a shaker, and then at room temperature. Leave for 3 days. Next, 10 ml of acetonitrile was added, shaken at 120 rpm at 25 ° C. for 30 minutes, and about 10 ⁇ l of the extract obtained by filtration through a membrane filter (0.45 ⁇ m) was injected into the HPLC for analysis. The amount of peroxide can be set.
- the pressure-sensitive adhesive composition of the present invention can contain a silane coupling agent (D).
- the durability can be improved by using the silane coupling agent (D).
- the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3, Epoxy group-containing silane coupling agents such as 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl- Amino group-containing silane coupling agents such as N- (1,3-dimethylbutylidene) propylamine, N-phenyl- ⁇ -aminopropyltrimethoxysilane, 3-acryloxypropyltrimeth
- the silane coupling agent (D) may be used singly or as a mixture of two or more, but the total content is the aromatic ring-containing (meth) acrylic polymer.
- the silane coupling agent is preferably 0.001 to 5 parts by weight, more preferably 0.01 to 1 part by weight, further preferably 0.02 to 1 part by weight, more preferably 100 parts by weight. Is preferably 0.05 to 0.6 parts by weight. This is an amount that improves the durability and appropriately maintains the adhesive force to an optical member such as a liquid crystal cell.
- polyether-modified silicone (E) can be blended in the pressure-sensitive adhesive composition of the present invention.
- the polyether-modified silicone (E) for example, those disclosed in JP 2010-275522 A can be used.
- the polyether-modified silicone (E) has a polyether skeleton, and at least one terminal has the following general formula (3): —SiR a M 3-a (Wherein R is an optionally substituted monovalent organic group having 1 to 20 carbon atoms, M is a hydroxyl group or a hydrolyzable group, and a is an integer of 0 to 2)
- R is an optionally substituted monovalent organic group having 1 to 20 carbon atoms
- M is a hydroxyl group or a hydrolyzable group
- a is an integer of 0 to 2
- the plurality of R may be the same or different from each other
- the plurality of M may be the same or different from each other. It has a reactive silyl group represented.
- R a M 3-a Si—XY— (AO) n —Z (Wherein R is an optionally substituted monovalent organic group having 1 to 20 carbon atoms, M is a hydroxyl group or a hydrolyzable group, and a is an integer of 0 to 2)
- R is an optionally substituted monovalent organic group having 1 to 20 carbon atoms
- M is a hydroxyl group or a hydrolyzable group
- a is an integer of 0 to 2
- the plurality of R may be the same or different from each other
- the plurality of M may be the same or different from each other.
- Z is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms
- R, M, X, Y, and a are the same as above.
- OA is the same as the above AO
- n is the same as above.
- Q is a divalent or higher hydrocarbon group having 1 to 10 carbon atoms.
- M is the same as the valence of the hydrocarbon group.) ).
- polyether-modified silicone (E) examples include, for example, MS polymer S203, S303, S810; SILYL EST250, EST280; Silyl SAT10, Silyl SAT200, Silyl SAT220, Silyl SAT350, Silyl SAT400, manufactured by Asahi Glass Co., Ltd. EXCESTAR S2410, S2420 or S3430.
- the pressure-sensitive adhesive composition of the present invention may contain other known additives, such as powders such as colorants and pigments, dyes, surfactants, plasticizers, tackifiers, Use surface lubricants, leveling agents, softeners, antioxidants, anti-aging agents, light stabilizers, UV absorbers, polymerization inhibitors, inorganic or organic fillers, metal powders, particles, foils, etc. It can be added appropriately depending on the application. Moreover, you may employ
- the pressure-sensitive adhesive composition forms a pressure-sensitive adhesive layer.
- it is necessary to fully consider the influence of the crosslinking treatment temperature and the crosslinking treatment time as well as adjusting the addition amount of the entire crosslinking agent. preferable.
- the crosslinking treatment temperature and crosslinking treatment time can be adjusted depending on the crosslinking agent used.
- the crosslinking treatment temperature is preferably 170 ° C. or lower.
- crosslinking treatment may be performed at the temperature during the drying step of the pressure-sensitive adhesive layer, or may be performed by providing a separate crosslinking treatment step after the drying step.
- the crosslinking treatment time can be set in consideration of productivity and workability, but is usually about 0.2 to 20 minutes, preferably about 0.5 to 10 minutes.
- the polarizing film with a pressure-sensitive adhesive layer of the present invention is one in which a pressure-sensitive adhesive layer is formed on at least one surface of the polarizing film with the pressure-sensitive adhesive composition.
- the pressure-sensitive adhesive layer for example, a method in which the pressure-sensitive adhesive composition is applied to a release-treated separator, and the polymerization solvent is dried and removed to form a pressure-sensitive adhesive layer, and then transferred to a polarizing film, or
- the pressure-sensitive adhesive composition is prepared by applying the pressure-sensitive adhesive composition to a polarizing film, drying and removing the polymerization solvent, and forming a pressure-sensitive adhesive layer on the polarizing film.
- one or more solvents other than the polymerization solvent may be added as appropriate.
- a silicone release liner is preferably used as the release-treated separator.
- a method for drying the pressure-sensitive adhesive is appropriately employed depending on the purpose. obtain.
- a method of heating and drying the coating film is used.
- the heating and drying temperature is preferably 40 ° C to 200 ° C, more preferably 50 ° C to 180 ° C, and particularly preferably 70 ° C to 170 ° C.
- the drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, and particularly preferably 10 seconds to 5 minutes.
- the pressure-sensitive adhesive layer can be formed after forming an anchor layer on the surface of the polarizing film or performing various easy adhesion treatments such as corona treatment and plasma treatment. Moreover, you may perform an easily bonding process on the surface of an adhesive layer.
- Various methods are used as a method for forming the pressure-sensitive adhesive layer. Specifically, for example, roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, die coater, etc. Examples thereof include an extrusion coating method.
- the thickness of the pressure-sensitive adhesive layer is not particularly limited, and is, for example, about 1 to 100 ⁇ m.
- the thickness is preferably 2 to 50 ⁇ m, more preferably 2 to 40 ⁇ m, and still more preferably 5 to 35 ⁇ m.
- the pressure-sensitive adhesive layer When the pressure-sensitive adhesive layer is exposed, the pressure-sensitive adhesive layer may be protected with a peeled sheet (separator) until practical use.
- constituent material of the separator examples include, for example, plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, porous materials such as paper, cloth, and nonwoven fabric, nets, foam sheets, metal foils, and laminates thereof.
- plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films
- porous materials such as paper, cloth, and nonwoven fabric, nets, foam sheets, metal foils, and laminates thereof.
- a plastic film is used suitably from the point which is excellent in surface smoothness.
- the plastic film is not particularly limited as long as it can protect the pressure-sensitive adhesive layer.
- a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, and a vinyl chloride co-polymer are used.
- examples thereof include a polymer film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, and an ethylene-vinyl acetate copolymer film.
- the thickness of the separator is usually about 5 to 200 ⁇ m, preferably about 5 to 100 ⁇ m.
- mold release and antifouling treatment with a silicone type, fluorine type, long chain alkyl type or fatty acid amide type release agent, silica powder, etc., coating type, kneading type, vapor deposition type It is also possible to carry out antistatic treatment such as.
- the release property from the pressure-sensitive adhesive layer can be further improved by appropriately performing a release treatment such as silicone treatment, long-chain alkyl treatment, or fluorine treatment on the surface of the separator.
- seat which carried out the peeling process used in preparation of said polarizing film with an adhesive layer can be used as a separator of the polarizing film with an adhesive layer as it is, and can simplify in the surface of a process.
- the polarizing film with a pressure-sensitive adhesive layer according to the present invention has at least a polarizing film and the pressure-sensitive adhesive layer described above, and the polarizing film generally has a transparent protective film on one or both sides of a polarizer. Used.
- the polarizer is not particularly limited, and various types can be used.
- polarizers include dichroic iodine and dichroic dyes on hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films.
- hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films.
- examples thereof include polyene-based oriented films such as those obtained by adsorbing substances and uniaxially stretched, polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochlorinated products.
- a polarizer composed of a polyvinyl alcohol film and a dichroic material such as iodine is preferable.
- the thickness of these polarizers is not particularly limited, but is generally about 80 ⁇ m or less.
- a polarizer in which a polyvinyl alcohol film is dyed with iodine and uniaxially stretched can be prepared, for example, by dyeing polyvinyl alcohol in an aqueous solution of iodine and stretching it 3 to 7 times the original length. If necessary, it can be immersed in an aqueous solution such as potassium iodide which may contain boric acid, zinc sulfate, zinc chloride or the like. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing.
- Stretching may be performed after dyeing with iodine, may be performed while dyeing, or may be dyed with iodine after stretching.
- the film can be stretched even in an aqueous solution such as boric acid or potassium iodide or in a water bath.
- a thin polarizer having a thickness of 10 ⁇ m or less can be used. From the viewpoint of thinning, the thickness is preferably 1 to 7 ⁇ m. Such a thin polarizer is preferable in that the thickness unevenness is small, the visibility is excellent, the dimensional change is small, the durability is excellent, and the thickness of the polarizing film can be reduced.
- the thin polarizer typically, JP-A-51-069644, JP-A-2000-338329, WO2010 / 100917, PCT / JP2010 / 001460, or Japanese Patent Application No. 2010- And a thin polarizing film described in Japanese Patent Application No. 269002 and Japanese Patent Application No. 2010-263692.
- These thin polarizing films can be obtained by a production method including a step of stretching a polyvinyl alcohol-based resin (hereinafter also referred to as PVA-based resin) layer and a stretching resin base material in a laminated state and a step of dyeing. With this manufacturing method, even if the PVA-based resin layer is thin, it can be stretched without problems such as breakage due to stretching by being supported by the stretching resin substrate.
- PVA-based resin polyvinyl alcohol-based resin
- the thin polarizing film among the production methods including the step of stretching in the state of a laminate and the step of dyeing, WO2010 / 100917 pamphlet, PCT / PCT / PCT / JP 2010/001460 specification, or Japanese Patent Application No. 2010-269002 and Japanese Patent Application No. 2010-263692, the one obtained by a production method including a step of stretching in a boric acid aqueous solution is preferable. What is obtained by the manufacturing method including the process of extending
- the thin high-performance polarizing film described in the specification of PCT / JP2010 / 001460 is a thin film having a thickness of 7 ⁇ m or less made of a PVA-based resin oriented with a dichroic material, which is integrally formed on a resin base material. It is a high-functional polarizing film, and has optical properties such as a single transmittance of 42.0% or more and a degree of polarization of 99.95% or more.
- the thin high-performance polarizing film generates a PVA-based resin layer by applying and drying a PVA-based resin on a resin substrate having a thickness of at least 20 ⁇ m, and the generated PVA-based resin layer is used as a dichroic dyeing solution. So that the dichroic substance is adsorbed on the PVA resin layer, and the PVA resin layer on which the dichroic substance is adsorbed is integrated with the resin base material in the boric acid aqueous solution so that the total draw ratio is the original length. It can manufacture by extending
- a method for producing a laminate film including a thin high-performance polarizing film in which a dichroic substance is oriented and includes a resin base material having a thickness of at least 20 ⁇ m and a PVA resin on one side of the resin base material.
- surface of the resin base material A step of adsorbing the dichroic substance to the PVA resin layer contained in the laminate film by immersing the film in a dye solution containing the dichroic substance, and a PVA resin adsorbing the dichroic substance
- the polarizing film with the pressure-sensitive adhesive layer is a continuous web polarizing film made of a PVA resin in which a dichroic substance is oriented as a polarizer having a thickness of 10 ⁇ m or less, What was obtained by extending
- stretching process which consists of air auxiliary
- the thermoplastic resin substrate is preferably an amorphous ester thermoplastic resin substrate or a crystalline ester thermoplastic resin substrate.
- the thin polarizing films in the above-mentioned Japanese Patent Application Nos. 2010-269002 and 2010-263692 are continuous web polarizing films made of a PVA-based resin in which a dichroic material is oriented, and are amorphous.
- the laminate including the PVA-based resin layer formed on the ester-based thermoplastic resin base material was stretched in a two-stage stretching process consisting of air-assisted stretching and boric acid-water stretching, so that the thickness was 10 ⁇ m or less. Is.
- Such a thin polarizing film has P> ⁇ (10 0.929 T ⁇ 42.4 ⁇ 1) ⁇ 100 (where T ⁇ 42.3) and P ⁇ , where T is the single transmittance and P is the polarization degree. It is preferable that the optical properties satisfy 99.9 (where T ⁇ 42.3).
- the thin polarizing film is a stretch intermediate formed of an oriented PVA resin layer by high-temperature stretching in the air with respect to the PVA resin layer formed on the amorphous ester thermoplastic resin substrate of the continuous web.
- a colored intermediate product comprising a PVA-based resin layer in which a dichroic material (preferably iodine or a mixture of iodine and an organic dye) is oriented by adsorption of the dichroic material to the stretched intermediate product and a step of generating the product.
- a thin polarizing film comprising: a step of producing a product; and a step of producing a polarizing film having a thickness of 10 ⁇ m or less comprising a PVA resin layer in which a dichroic substance is oriented by stretching in a boric acid solution with respect to a colored intermediate product It can manufacture with the manufacturing method of.
- the total draw ratio of the PVA resin layer formed on the amorphous ester thermoplastic resin base material by high-temperature drawing in air and drawing in boric acid solution should be 5 times or more. desirable.
- stretching can be 60 degreeC or more.
- the colored intermediate product is added to the aqueous boric acid solution whose liquid temperature does not exceed 40 ° C. It is desirable to do so by dipping.
- the amorphous ester-based thermoplastic resin base material is amorphous polyethylene containing copolymerized polyethylene terephthalate copolymerized with isophthalic acid, copolymerized polyethylene terephthalate copolymerized with cyclohexanedimethanol, or other copolymerized polyethylene terephthalate. It can be terephthalate and is preferably made of a transparent resin, and the thickness thereof can be 7 times or more the thickness of the PVA resin layer to be formed.
- the draw ratio of high-temperature drawing in the air is preferably 3.5 times or less, and the drawing temperature of high-temperature drawing in the air is preferably not less than the glass transition temperature of the PVA resin, specifically in the range of 95 ° C to 150 ° C.
- the total stretching ratio of the PVA resin layer formed on the amorphous ester thermoplastic resin base material is preferably 5 to 7.5 times .
- the total stretching ratio of the PVA-based resin layer formed on the amorphous ester-based thermoplastic resin base material is 5 times or more and 8.5 times or less. Is preferred. More specifically, a thin polarizing film can be produced by the following method.
- a base material for a continuous web of isophthalic acid copolymerized polyethylene terephthalate (amorphous PET) in which 6 mol% of isophthalic acid is copolymerized is prepared.
- the glass transition temperature of amorphous PET is 75 ° C.
- a laminate comprising a continuous web of amorphous PET substrate and a polyvinyl alcohol (PVA) layer is prepared as follows. Incidentally, the glass transition temperature of PVA is 80 ° C.
- a 200 ⁇ m-thick amorphous PET base material and a 4-5% PVA aqueous solution in which PVA powder having a polymerization degree of 1000 or more and a saponification degree of 99% or more are dissolved in water are prepared.
- an aqueous PVA solution is applied to a 200 ⁇ m thick amorphous PET substrate and dried at a temperature of 50 to 60 ° C. to obtain a laminate in which a 7 ⁇ m thick PVA layer is formed on the amorphous PET substrate. .
- a thin and highly functional polarizing film having a thickness of 3 ⁇ m is manufactured from the laminate including the PVA layer having a thickness of 7 ⁇ m through the following steps including a two-stage stretching process of air-assisted stretching and boric acid water stretching.
- the laminate including the 7 ⁇ m-thick PVA layer is integrally stretched with the amorphous PET substrate to produce a stretched laminate including the 5 ⁇ m-thick PVA layer.
- a laminate including a 7 ⁇ m-thick PVA layer is subjected to a stretching apparatus disposed in an oven set to a stretching temperature environment of 130 ° C. so that the stretching ratio is 1.8 times. Are stretched uniaxially at the free end.
- the PVA layer contained in the stretched laminate is changed to a 5 ⁇ m thick PVA layer in which PVA molecules are oriented.
- this colored laminate has a single layer transmittance of the PVA layer constituting the high-performance polarizing film that is finally produced by using the stretched laminate in a staining solution containing iodine and potassium iodide at a liquid temperature of 30 ° C.
- Iodine is adsorbed to the PVA layer contained in the stretched laminate by dipping for an arbitrary period of time so as to be 40 to 44%.
- the staining solution uses water as a solvent, and an iodine concentration within the range of 0.12 to 0.30% by weight and a potassium iodide concentration within the range of 0.7 to 2.1% by weight.
- concentration ratio of iodine and potassium iodide is 1 to 7.
- potassium iodide is required to dissolve iodine in water. More specifically, by immersing the stretched laminate in a dyeing solution having an iodine concentration of 0.30% by weight and a potassium iodide concentration of 2.1% by weight for 60 seconds, iodine is applied to a 5 ⁇ m-thick PVA layer in which PVA molecules are oriented. A colored laminate is adsorbed on the substrate.
- the colored laminated body is further stretched integrally with the amorphous PET base material by the second stage boric acid underwater stretching step to produce an optical film laminate including a PVA layer constituting a highly functional polarizing film having a thickness of 3 ⁇ m.
- the optical film laminate is subjected to stretching by applying the colored laminate to a stretching apparatus provided in a treatment apparatus set to a boric acid aqueous solution having a liquid temperature range of 60 to 85 ° C. containing boric acid and potassium iodide. It is stretched uniaxially at the free end so that the magnification is 3.3 times. More specifically, the liquid temperature of the boric acid aqueous solution is 65 ° C.
- the colored laminate having an adjusted iodine adsorption amount is first immersed in an aqueous boric acid solution for 5 to 10 seconds. After that, the colored laminate is passed as it is between a plurality of sets of rolls having different peripheral speeds, which is a stretching apparatus installed in the processing apparatus, and the stretching ratio can be freely increased to 3.3 times over 30 to 90 seconds. Stretch uniaxially.
- the PVA layer contained in the colored laminate is changed into a PVA layer having a thickness of 3 ⁇ m in which the adsorbed iodine is oriented higher in one direction as a polyiodine ion complex.
- This PVA layer constitutes a highly functional polarizing film of the optical film laminate.
- the optical film laminate was removed from the boric acid aqueous solution and adhered to the surface of the 3 ⁇ m-thick PVA layer formed on the amorphous PET substrate by the washing step. It is preferable to wash boric acid with an aqueous potassium iodide solution. Thereafter, the washed optical film laminate is dried by a drying process using hot air at 60 ° C.
- the cleaning process is a process for eliminating appearance defects such as boric acid precipitation.
- an adhesive is applied to the surface of a 3 ⁇ m-thick PVA layer formed on an amorphous PET substrate by a bonding and / or transfer process.
- the amorphous PET substrate can be peeled off, and the 3 ⁇ m thick PVA layer can be transferred to the 80 ⁇ m thick triacetyl cellulose film.
- the manufacturing method of said thin-shaped polarizing film may include another process other than the said process.
- Examples of other steps include an insolubilization step, a crosslinking step, and a drying (adjustment of moisture content) step.
- the other steps can be performed at any appropriate timing.
- the insolubilization step is typically performed by immersing the PVA resin layer in a boric acid aqueous solution. By performing the insolubilization treatment, water resistance can be imparted to the PVA resin layer.
- the concentration of the boric acid aqueous solution is preferably 1 to 4 parts by weight with respect to 100 parts by weight of water.
- the liquid temperature of the insolubilizing bath (boric acid aqueous solution) is preferably 20 ° C.
- the insolubilization step is performed after the laminate is manufactured and before the dyeing step and the underwater stretching step.
- the crosslinking step is typically performed by immersing the PVA resin layer in an aqueous boric acid solution.
- the concentration of the boric acid aqueous solution is preferably 1 to 4 parts by weight with respect to 100 parts by weight of water.
- blend iodide it is preferable to mix
- the blending amount of iodide is preferably 1 to 5 parts by weight with respect to 100 parts by weight of water. Specific examples of the iodide are as described above.
- the liquid temperature of the crosslinking bath is preferably 20 ° C. to 50 ° C.
- the crosslinking step is performed before the second boric acid aqueous drawing step.
- the dyeing step, the crosslinking step, and the second boric acid aqueous drawing step are performed in this order.
- thermoplastic resin excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like is used.
- thermoplastic resins include cellulose resins such as triacetyl cellulose, polyester resins, polyethersulfone resins, polysulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins, cyclic Examples thereof include polyolefin resins (norbornene resins), polyarylate resins, polystyrene resins, polyvinyl alcohol resins, and mixtures thereof.
- a transparent protective film is bonded to one side of the polarizer by an adhesive layer.
- thermosetting resin such as a system or an ultraviolet curable resin
- a thermosetting resin such as a system or an ultraviolet curable resin
- the additive include an ultraviolet absorber, an antioxidant, a lubricant, a plasticizer, a mold release agent, an anti-coloring agent, a flame retardant, a nucleating agent, an antistatic agent, a pigment, and a coloring agent.
- the content of the thermoplastic resin in the transparent protective film is preferably 50 to 100% by weight, more preferably 50 to 99% by weight, still more preferably 60 to 98% by weight, and particularly preferably 70 to 97% by weight. .
- content of the said thermoplastic resin in a transparent protective film is 50 weight% or less, there exists a possibility that the high transparency etc. which a thermoplastic resin originally has cannot fully be expressed.
- An adhesive is used for the adhesion treatment between the polarizer and the transparent protective film.
- the adhesive include isocyanate adhesives, polyvinyl alcohol adhesives, gelatin adhesives, vinyl latexes, and water-based polyesters.
- the adhesive is usually used as an adhesive made of an aqueous solution, and usually contains 0.5 to 60% by weight of a solid content.
- examples of the adhesive between the polarizer and the transparent protective film include an ultraviolet curable adhesive and an electron beam curable adhesive.
- the electron beam curable polarizing film adhesive exhibits suitable adhesiveness to the various transparent protective films.
- the adhesive used by this invention can be made to contain a metal compound filler.
- the polarizing film can be laminated with other optical films.
- other optical films include the formation of liquid crystal display devices such as reflectors, anti-transmission plates, retardation plates (including wavelength plates such as 1/2 and 1/4), visual compensation films, and brightness enhancement films.
- the thing used as the optical layer which may be used is mentioned. These can be laminated on the polarizing film for practical use, and one layer or two or more layers can be used.
- An optical film obtained by laminating the optical layer on a polarizing film can be formed by a method of laminating separately sequentially in the manufacturing process of a liquid crystal display device or the like. It is excellent in stability and assembly work, and has the advantage of improving the manufacturing process of a liquid crystal display device and the like.
- Appropriate bonding means such as an adhesive layer can be used for lamination. When adhering the polarizing film and the other optical layer, their optical axes can be set at an appropriate arrangement angle in accordance with a target retardation characteristic or the like.
- the polarizing film with an adhesive layer of the present invention can be preferably used for forming various image display devices such as a liquid crystal display device.
- the liquid crystal display device can be formed according to the conventional method. That is, a liquid crystal display device is generally formed by appropriately assembling components such as a display panel such as a liquid crystal cell, a polarizing film with an adhesive layer, and an illumination system as necessary, and incorporating a drive circuit.
- a display panel such as a liquid crystal cell
- a polarizing film with an adhesive layer such as a liquid crystal cell
- an illumination system as necessary
- an arbitrary type such as an arbitrary type such as a TN type, STN type, ⁇ type, VA type, or IPS type can be used.
- liquid crystal display devices such as a liquid crystal display device in which a polarizing film with an adhesive layer is disposed on one side or both sides of a display panel such as a liquid crystal cell, or a lighting system using a backlight or a reflector can be formed.
- the polarizing film with an adhesive layer by this invention can be installed in the one side or both sides of display panels, such as a liquid crystal cell.
- optical films are provided on both sides, they may be the same or different.
- a single layer or a suitable part such as a diffusion plate, an antiglare layer, an antireflection film, a protective plate, a prism array, a lens array sheet, a light diffusion plate, a backlight, Two or more layers can be arranged.
- ⁇ Creation of polarizing film (1)> A 80 ⁇ m-thick polyvinyl alcohol film was stretched up to 3 times between rolls with different speed ratios while being dyed in an iodine solution of 0.3% concentration at 30 ° C. for 1 minute. Thereafter, the film was stretched so that the total stretch ratio was 6 times while being immersed in an aqueous solution containing 60% at 4% concentration of boric acid and 10% concentration of potassium iodide for 0.5 minutes. Next, after washing by immersing in an aqueous solution containing potassium iodide at 30 ° C. and 1.5% concentration for 10 seconds, drying was performed at 50 ° C. for 4 minutes to obtain a polarizer having a thickness of 20 ⁇ m.
- TAC polarizing film (1) A saponified 40 ⁇ m thick triacetyl cellulose film was bonded to both surfaces of the polarizer with a polyvinyl alcohol-based adhesive, respectively, to prepare polarizing films.
- this is referred to as a TAC polarizing film (1).
- ⁇ Creation of polarizing film (2)> In order to produce a thin polarizing film, first, a laminated body in which a PVA layer having a thickness of 9 ⁇ m is formed on an amorphous PET substrate is produced by air-assisted stretching at a stretching temperature of 130 ° C., and then stretched. A colored laminate is produced by dyeing the laminate, and the colored laminate is further stretched integrally with an amorphous PET substrate so that the total draw ratio is 5.94 times by stretching in boric acid water at a stretching temperature of 65 degrees. An optical film laminate including a 4 ⁇ m thick PVA layer was produced.
- the PVA molecules in the PVA layer formed on the amorphous PET substrate by such two-stage stretching are oriented in the higher order, and the iodine adsorbed by the dyeing is oriented in the one direction as the polyiodine ion complex. It was possible to produce an optical film laminate including a PVA layer having a thickness of 4 ⁇ m and constituting a highly functional polarizing film. Further, after applying a saponified 40 ⁇ m thick acrylic resin film while applying a polyvinyl alcohol adhesive on the surface of the polarizing film of the optical film laminate, the amorphous PET substrate was peeled off, A polarizing film using the film was prepared. Hereinafter, this is referred to as a thin polarizing film (2).
- a laminated body in which a PVA layer having a thickness of 9 ⁇ m is formed on an amorphous PET substrate is produced by air-assisted stretching at a stretching temperature of 130 ° C., and then stretched.
- a colored laminate is produced by dyeing the laminate, and the colored laminate is further stretched integrally with an amorphous PET substrate so that the total draw ratio is 5.94 times by stretching in boric acid water at a stretching temperature of 65 degrees.
- An optical film laminate including a 4 ⁇ m thick PVA layer was produced.
- the PVA molecules in the PVA layer formed on the amorphous PET substrate by such two-stage stretching are oriented in the higher order, and the iodine adsorbed by the dyeing is oriented in the one direction as the polyiodine ion complex. It was possible to produce an optical film laminate including a PVA layer having a thickness of 4 ⁇ m and constituting a highly functional polarizing film.
- a thin polarizing film (3) After applying the polyvinyl alcohol adhesive to the surface of the polarizing film of the optical film laminate, after laminating the saponified 40 ⁇ m thick triacetyl cellulose film, after peeling the amorphous PET substrate, A norbornene-based film having a thickness of 33 ⁇ m was bonded to the other surface with a polyvinyl alcohol-based adhesive, thereby producing a polarizing film using a thin polarizing film.
- this is referred to as a thin polarizing film (3).
- Production Example 1 ⁇ Preparation of aromatic ring-containing (meth) acrylic polymer (A-1)>
- a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirring device 90 parts of butyl acrylate, 5 parts of benzyl acrylate (BzA), 5 parts of 4-hydroxybutyl acrylate, and AIBN as a monomer (Solid content) 1 part per 100 parts is added with ethyl acetate and reacted at 60 ° C. for 7 hours under a nitrogen gas stream. Then, ethyl acetate is added to the reaction solution to give an aromatic having a weight average molecular weight of 1,200,000.
- a solution containing the ring-containing (meth) acrylic polymer (A-1) was obtained (solid content concentration 30% by weight).
- Production Example 2 ⁇ Preparation of aromatic ring-containing (meth) acrylic polymer (A-2)>
- a weight average was obtained in the same manner as in Production Example 1 except that a monomer mixture containing 87 parts of butyl acrylate, 10 parts of benzyl acrylate, and 3 parts of 4-hydroxybutyl acrylate was used as the monomer mixture.
- Production Example 3 ⁇ Preparation of aromatic ring-containing (meth) acrylic polymer (A-3)>
- a weight average was obtained in the same manner as in Production Example 1 except that a monomer mixture containing 82 parts of butyl acrylate, 15 parts of benzyl acrylate, and 3 parts of 4-hydroxybutyl acrylate was used as the monomer mixture.
- Production Example 4 ⁇ Preparation of aromatic ring-containing (meth) acrylic polymer (A-4)> In Production Example 1, the same as in Production Example 1, except that a monomer mixture containing 77 parts of butyl acrylate, 20 parts of benzyl acrylate, and 3 parts of 4-hydroxybutyl acrylate was used as the monomer mixture. A solution of an aromatic ring-containing (meth) acrylic polymer (A-4) having a molecular weight of 1.35 million was prepared.
- Production Example 5 ⁇ Preparation of aromatic ring-containing (meth) acrylic polymer (A-5)>
- a weight average was obtained in the same manner as in Production Example 1 except that a monomer mixture containing 72 parts of butyl acrylate, 25 parts of benzyl acrylate, and 3 parts of 4-hydroxybutyl acrylate was used as the monomer mixture.
- a solution of an aromatic ring-containing (meth) acrylic polymer (A-5) having a molecular weight of 1,200,000 was prepared.
- Production Example 6 Preparation of aromatic ring-containing (meth) acrylic polymer (A-6)>
- a weight average was obtained in the same manner as in Production Example 1 except that a monomer mixture containing 67 parts of butyl acrylate, 30 parts of benzyl acrylate, and 3 parts of 4-hydroxybutyl acrylate was used as the monomer mixture.
- a solution of an aromatic ring-containing (meth) acrylic polymer (A-6) having a molecular weight of 1,200,000 was prepared.
- Production Example 7 ⁇ Preparation of aromatic ring-containing (meth) acrylic polymer (A-7)>
- the same procedure as in Production Example 1 was used, except that a monomer mixture containing 82 parts of butyl acrylate, 15 parts of phenoxyethyl acrylate (PEA), and 3 parts of 4-hydroxybutyl acrylate was used. Then, a solution of an aromatic ring-containing (meth) acrylic polymer (A-7) having a weight average molecular weight of 1.3 million was prepared.
- Production Example 8 ⁇ Preparation of aromatic ring-containing (meth) acrylic polymer (A-8)>
- the same weight as in Production Example 1 was used, except that a monomer mixture containing 77 parts of butyl acrylate, 20 parts of phenoxyethyl acrylate, and 3 parts of 4-hydroxybutyl acrylate was used as the monomer mixture.
- Example 1 (Preparation of adhesive composition) 0.1 part of trimethylolpropan xylylene diisocyanate (manufactured by Mitsui Chemicals, Inc .: Takenate D110N per 100 parts of solid content of the aromatic ring-containing (meth) acrylic polymer (A-1) solution obtained in Production Example 1 ), 0.3 part of dibenzoyl peroxide, 0.1 part of ⁇ -glycidoxypropylmethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-403), and bis (nonafluorobutanesulfonyl) imide lithium 1 part (trade name “EF-N445”, manufactured by Mitsubishi Materials Electronic Chemical Co., Ltd.) was blended to obtain an acrylic pressure-sensitive adhesive solution.
- Trimethylolpropan xylylene diisocyanate manufactured by Mitsui Chemicals, Inc .: Takenate D110N per 100 parts of solid content of the aromatic ring-containing (me
- the pressure-sensitive adhesive solution is uniformly coated on the surface of a polyethylene terephthalate film (base material) treated with a silicone-based release agent with a fountain coater, dried in an air circulation type thermostatic oven at 155 ° C. for 2 minutes, A pressure-sensitive adhesive layer having a thickness of 20 ⁇ m was formed on the surface. Subsequently, the separator which formed the adhesive layer was transferred to the TAC polarizing film (1), and the optical film with an adhesive layer was produced.
- Example 1 preparation of the pressure-sensitive adhesive composition was carried out in the same manner as in Example 1 except that the amount of each component used was changed as shown in Tables 1 and 2 or the type of polarizing film was changed. Thus, a polarizing film with an adhesive layer was produced.
- ⁇ Surface resistance value Initial resistance value> After removing the separator film of the polarizing film with the pressure-sensitive adhesive layer, the surface resistance value ( ⁇ / ⁇ ) of the pressure-sensitive adhesive surface was measured using MCP-HT450 manufactured by Mitsubishi Chemical Analytech.
- ⁇ Surface resistance value: resistance value after humidification test> The polarizing film with the pressure-sensitive adhesive layer obtained in Examples and Comparative Examples was put into a constant temperature and humidity chamber of 60 ° C./95% RH, taken out after 48 hours, dried at 60 ° C. for 2 hours, and then peeled off the separator film.
- the surface resistance value of the pressure-sensitive adhesive surface was measured using MCP-HT450 manufactured by Mitsubishi Chemical Analytech Co., Ltd.
- B-1 in the ionic compound (B) is bis (nonafluorobutanesulfonyl) imidolithium (trade name “EF-N445”, manufactured by Mitsubishi Materials Electronic Chemicals), “B -2 ”is bis (heptafluoropropanesulfonyl) imide lithium (manufactured by Wako Pure Chemical Industries, Ltd.), and“ B-3 ”is cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide lithium (trade name“ EF- ”).
- B-4 is 1-butyl-3-methylpyridinium bis (nonafluorobutanesulfonyl) imide (trade name” BuMePy ⁇ N441 ", manufactured by Mitsubishi Materials Electronic Chemicals)
- B-5 is bis (trifluoromethanesulfonyl) imide lithium (manufactured by Wako Pure Chemical Industries, Ltd.)
- B-6 is 1-butyl -3-Methylpyridinium bis (trifluoromethanesulfonyl) imide (trade name “CIL-312”, manufactured by Nippon Carlit)
- B-7 is 1,1,2,2,3,3-hexafluoropropane- 1,3-disulfonic acid dilithium salt (trade name “EF-3005”, manufactured by Mitsubishi Materials Electronic Chemical Co., Ltd.)
- B-8 represents ethylmethylpyrrolidinium bis (trifluoromethanesulfon
- C-1 is an isocyanate cross-linking agent (trade name “Takenate D110N”, trimethylolpropane xylylene diisocyanate) manufactured by Mitsui Chemicals Polyurethanes
- C-2 is a distillate manufactured by Nippon Oil & Fats Co., Ltd. Benzoyl peroxide (Nyper BMT) is shown.
- D-1 in the silane coupling agent (D) represents KBM403 manufactured by Shin-Etsu Chemical Co., Ltd.
- E-1 indicates (trade name “Syryl SAT10”, manufactured by Kaneka Corporation
- E-2 indicates (trade name “SIB1824.82”, manufactured by GELEST).
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Abstract
Description
(CnF2n+1SO2)2N- (1)
(一般式(1)中、nは1~10の整数)、下記一般式(2):
CF2(CmF2mSO2)2N- (2)
(一般式(2)中、mは2~10の整数):および下記一般式(3):
-O3S(CF2)l SO3 - (3)
(一般式(3)中、lは3~10の整数)で表される少なくとも1種のアニオン成分であることが好ましい。 In the pressure-sensitive adhesive composition, the anion component is represented by the following general formula (1):
(C n F 2n + 1 SO 2 ) 2 N − (1)
(In the general formula (1), n is an integer of 1 to 10), the following general formula (2):
CF 2 (C m F 2m SO 2 ) 2 N − (2)
(In the general formula (2), m is an integer of 2 to 10): and the following general formula (3):
- O 3 S (CF 2) l SO 3 - (3)
It is preferable that at least one anion component represented by (in general formula (3), l is an integer of 3 to 10).
本発明においては、アニオン成分が、下記一般式(1):
(CnF2n+1SO2)2N- (1)
(一般式(1)中、nは1~10の整数)、下記一般式(2):
CF2(CmF2mSO2)2N- (2)
(一般式(2)中、mは2~10の整数):および下記一般式(3):
-O3S(CF2)l SO3 - (3)
(一般式(3)中、lは3~10の整数)で表される少なくとも1種のアニオン成分である場合、芳香族環含有(メタ)アクリル系ポリマー(A)と併用することにより、粘着剤としての耐久性の低下を著しく抑制しつつ、帯電防止機能を付与できるため、好ましい。 (Anionic component of ionic compound (B))
In the present invention, the anion component is represented by the following general formula (1):
(C n F 2n + 1 SO 2 ) 2 N − (1)
(In the general formula (1), n is an integer of 1 to 10), the following general formula (2):
CF 2 (C m F 2m SO 2 ) 2 N − (2)
(In the general formula (2), m is an integer of 2 to 10): and the following general formula (3):
- O 3 S (CF 2) l SO 3 - (3)
(In general formula (3), l is an integer of 3 to 10), and when used together with the aromatic ring-containing (meth) acrylic polymer (A), It is preferable because an antistatic function can be imparted while significantly lowering the durability as an agent.
イオン性化合物(B)のカチオン成分としては、リチウム、ナトリウム、カリウムのアルカリ金属イオンが挙げられ、上記のアニオン成分と共に、イオン性化合物(B)としてのアルカリ金属塩を構成する。アルカリ金属イオンのなかでも、カリウムイオンを有するイオン性化合物(B)を含有する粘着剤組成物から形成された粘着剤層では、初期の表面抵抗値が上昇する傾向にある。その一方で、リチウムイオンを有するイオン性化合物(B)を含有する場合、粘着剤層の初期の表面抵抗値および加湿後の表面抵抗値の上昇を抑制できる。 (Cation component of ionic compound (B))
Examples of the cation component of the ionic compound (B) include lithium, sodium, and potassium alkali metal ions, and together with the anion component, constitute an alkali metal salt as the ionic compound (B). Among the alkali metal ions, in the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition containing the ionic compound (B) having potassium ions, the initial surface resistance value tends to increase. On the other hand, when the ionic compound (B) having lithium ions is contained, an increase in the initial surface resistance value of the pressure-sensitive adhesive layer and the surface resistance value after humidification can be suppressed.
アニオン成分としては、CH3COO-、CF3COO-、CH3SO3 -、CF3SO3 -、(CF3SO2)2N-、(CF3SO2)3C-、C4F9SO3 -、(C2F5SO2)2N-、C3F7COO-、(CF3SO2)(CF3CO)N-、-O3S(CF2)3SO3 -、PF6 -、CO3 2-、などの有機物;Cl-、Br-、I-、AlCl4 -、Al2Cl7 -、BF4 -、PF6 -、ClO4 -、NO3 -、AsF6 -、SbF6 -、NbF6 -、TaF6-、(CN)2N-、などの無機物が挙げられる。上記アニオン成分の中でも、特に、フッ素原子を含むアニオン部は、イオン解離性の良いイオン化合物が得られることから好ましく、(CF3SO2)2N-、(C2F5SO2)2N-等の(ペルフルオロアルキルスルホニル)イミドがより好ましく、(CF3SO2)2N-、で表わされる(トリフルオロメタンスルホニル)イミドがさらに好ましい。 The alkali metal salt which has each ion of lithium, sodium, and potassium as a cation component, and the anion component shown below.
Examples of the anion component include CH 3 COO − , CF 3 COO − , CH 3 SO 3 − , CF 3 SO 3 − , (CF 3 SO 2 ) 2 N − , (CF 3 SO 2 ) 3 C − , C 4 F 9 SO 3 -, (C 2 F 5 SO 2) 2 N -, C 3 F 7 COO -, (CF 3 SO 2) (CF 3 CO) N -, - O 3 S (CF 2) 3 SO 3 - , PF 6 − , CO 3 2− , etc .; Cl − , Br − , I − , AlCl 4 − , Al 2 Cl 7 − , BF 4 − , PF 6 − , ClO 4 − , NO 3 − , AsF Examples thereof include inorganic substances such as 6 − , SbF 6 − , NbF 6 − , TaF 6− , (CN) 2 N − . Among the above anion components, an anion portion containing a fluorine atom is particularly preferable because an ionic compound having a good ion dissociation property is obtained. (CF 3 SO 2 ) 2 N − , (C 2 F 5 SO 2 ) 2 N (Perfluoroalkylsulfonyl) imide such as — is more preferable, and (trifluoromethanesulfonyl) imide represented by (CF 3 SO 2 ) 2 N − is more preferable.
(式中、Rは、置換基を有していてもよい、炭素数1~20の1価の有機基であり、Mは水酸基又は加水分解性基であり、aは0~2の整数である。但し、Rが複数存在するとき複数のRは互いに同一であっても異なっていてもよく、Mが複数存在するとき複数のMは互いに同一であっても異なっていてもよい。)で表される反応性シリル基を有する。 The polyether-modified silicone (E) has a polyether skeleton, and at least one terminal has the following general formula (3): —SiR a M 3-a
(Wherein R is an optionally substituted monovalent organic group having 1 to 20 carbon atoms, M is a hydroxyl group or a hydrolyzable group, and a is an integer of 0 to 2) However, when a plurality of R are present, the plurality of R may be the same or different from each other, and when a plurality of M are present, the plurality of M may be the same or different from each other. It has a reactive silyl group represented.
一般式(4):RaM3-aSi-X-Y-(AO)n-Z
(式中、Rは、置換基を有していてもよい、炭素数1~20の1価の有機基であり、Mは水酸基又は加水分解性基であり、aは0~2の整数である。但し、Rが複数存在するとき複数のRは互いに同一であっても異なっていてもよく、Mが複数存在するとき複数のMは互いに同一であっても異なっていてもよい。AOは、直鎖または分岐鎖の炭素数1~10のオキシアルキレン基を示し、nは1~1700であり、オキシアルキレン基の平均付加モル数を示す。Xは、炭素数1~20の直鎖または分岐鎖のアルキレン基を示す。Yは、エーテル結合、エステル結合、ウレタン結合、またはカーボネート結合を示す。
Zは、水素原子、1価の炭素数1~10の炭化水素基、
一般式(4A):-Y1-X-SiRaM3-a
(式中、R、M、X、aは、前記と同じ。Y1は単結合、-CO-結合、-CONH-結合、または-COO-結合を示す。)、または、
一般式(4B):-Q{-(OA)n-Y-X-SiRaM3-a}m
(式中、R、M、X、Y、aは、前記と同じ。OAは前記のAOに同じで、nは前記と同じ。Qは、2価以上の炭素数1~10の炭化水素基であり、mは当該炭化水素基の価数と同じ。)で表される基である。)で表される化合物が挙げられる。 As the polyether-modified silicone (E),
Formula (4): R a M 3-a Si—XY— (AO) n —Z
(Wherein R is an optionally substituted monovalent organic group having 1 to 20 carbon atoms, M is a hydroxyl group or a hydrolyzable group, and a is an integer of 0 to 2) However, when a plurality of R are present, the plurality of R may be the same or different from each other, and when a plurality of M are present, the plurality of M may be the same or different from each other. Represents a linear or branched oxyalkylene group having 1 to 10 carbon atoms, n is 1 to 1700, and represents an average number of added moles of the oxyalkylene group, X is a linear or branched chain having 1 to 20 carbon atoms, Y represents a branched alkylene group, and Y represents an ether bond, an ester bond, a urethane bond, or a carbonate bond.
Z is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms,
Formula (4A): —Y 1 —X—SiR a M 3-a
(Wherein R, M, X, and a are the same as defined above, Y 1 represents a single bond, —CO— bond, —CONH— bond, or —COO— bond), or
Formula (4B): -Q {-(OA) n -YX-SiR a M 3-a } m
(In the formula, R, M, X, Y, and a are the same as above. OA is the same as the above AO, n is the same as above. Q is a divalent or higher hydrocarbon group having 1 to 10 carbon atoms. M is the same as the valence of the hydrocarbon group.) ).
更に具体的には、次のような方法により、薄型偏光膜を製造することができる。 In this production method, the total draw ratio of the PVA resin layer formed on the amorphous ester thermoplastic resin base material by high-temperature drawing in air and drawing in boric acid solution should be 5 times or more. desirable. The liquid temperature of the boric acid aqueous solution for boric-acid water extending | stretching can be 60 degreeC or more. Before stretching the colored intermediate product in the aqueous boric acid solution, it is desirable to insolubilize the colored intermediate product. In this case, the colored intermediate product is added to the aqueous boric acid solution whose liquid temperature does not exceed 40 ° C. It is desirable to do so by dipping. The amorphous ester-based thermoplastic resin base material is amorphous polyethylene containing copolymerized polyethylene terephthalate copolymerized with isophthalic acid, copolymerized polyethylene terephthalate copolymerized with cyclohexanedimethanol, or other copolymerized polyethylene terephthalate. It can be terephthalate and is preferably made of a transparent resin, and the thickness thereof can be 7 times or more the thickness of the PVA resin layer to be formed. In addition, the draw ratio of high-temperature drawing in the air is preferably 3.5 times or less, and the drawing temperature of high-temperature drawing in the air is preferably not less than the glass transition temperature of the PVA resin, specifically in the range of 95 ° C to 150 ° C. When performing high temperature stretching in the air by free end uniaxial stretching, the total stretching ratio of the PVA resin layer formed on the amorphous ester thermoplastic resin base material is preferably 5 to 7.5 times . In addition, when performing high-temperature stretching in the air by uniaxial stretching at the fixed end, the total stretching ratio of the PVA-based resin layer formed on the amorphous ester-based thermoplastic resin base material is 5 times or more and 8.5 times or less. Is preferred.
More specifically, a thin polarizing film can be produced by the following method.
上記の薄型偏光膜の製造方法は、上記工程以外に、その他の工程を含み得る。その他の工程としては、例えば、不溶化工程、架橋工程、乾燥(水分率の調節)工程等が挙げられる。その他の工程は、任意の適切なタイミングで行い得る。
上記不溶化工程は、代表的には、ホウ酸水溶液にPVA系樹脂層を浸漬させることにより行う。不溶化処理を施すことにより、PVA系樹脂層に耐水性を付与することができる。当該ホウ酸水溶液の濃度は、水100重量部に対して、好ましくは1重量部~4重量部である。不溶化浴(ホウ酸水溶液)の液温は、好ましくは20℃~50℃である。好ましくは、不溶化工程は、積層体作製後、染色工程や水中延伸工程の前に行う。
上記架橋工程は、代表的には、ホウ酸水溶液にPVA系樹脂層を浸漬させることにより行う。架橋処理を施すことにより、PVA系樹脂層に耐水性を付与することができる。当該ホウ酸水溶液の濃度は、水100重量部に対して、好ましくは1重量部~4重量部である。また、上記染色工程後に架橋工程を行う場合、さらに、ヨウ化物を配合することが好ましい。ヨウ化物を配合することにより、PVA系樹脂層に吸着させたヨウ素の溶出を抑制することができる。ヨウ化物の配合量は、水100重量部に対して、好ましくは1重量部~5重量部である。ヨウ化物の具体例は、上述のとおりである。架橋浴(ホウ酸水溶液)の液温は、好ましくは20℃~50℃である。好ましくは、架橋工程は上記第2のホウ酸水中延伸工程の前に行う。好ましい実施形態においては、染色工程、架橋工程および第2のホウ酸水中延伸工程をこの順で行う。 [Other processes]
The manufacturing method of said thin-shaped polarizing film may include another process other than the said process. Examples of other steps include an insolubilization step, a crosslinking step, and a drying (adjustment of moisture content) step. The other steps can be performed at any appropriate timing.
The insolubilization step is typically performed by immersing the PVA resin layer in a boric acid aqueous solution. By performing the insolubilization treatment, water resistance can be imparted to the PVA resin layer. The concentration of the boric acid aqueous solution is preferably 1 to 4 parts by weight with respect to 100 parts by weight of water. The liquid temperature of the insolubilizing bath (boric acid aqueous solution) is preferably 20 ° C. to 50 ° C. Preferably, the insolubilization step is performed after the laminate is manufactured and before the dyeing step and the underwater stretching step.
The crosslinking step is typically performed by immersing the PVA resin layer in an aqueous boric acid solution. By performing the crosslinking treatment, water resistance can be imparted to the PVA resin layer. The concentration of the boric acid aqueous solution is preferably 1 to 4 parts by weight with respect to 100 parts by weight of water. Moreover, when performing a bridge | crosslinking process after the said dyeing | staining process, it is preferable to mix | blend iodide further. By blending iodide, elution of iodine adsorbed on the PVA resin layer can be suppressed. The blending amount of iodide is preferably 1 to 5 parts by weight with respect to 100 parts by weight of water. Specific examples of the iodide are as described above. The liquid temperature of the crosslinking bath (boric acid aqueous solution) is preferably 20 ° C. to 50 ° C. Preferably, the crosslinking step is performed before the second boric acid aqueous drawing step. In a preferred embodiment, the dyeing step, the crosslinking step, and the second boric acid aqueous drawing step are performed in this order.
芳香族環含有(メタ)アクリル系ポリマー(A)の重量平均分子量は、GPC(ゲル・パーミエーション・クロマトグラフィー)により測定した。
・分析装置:東ソー社製、HLC-8120GPC
・カラム:東ソー社製、G7000HXL+GMHXL+GMHXL
・カラムサイズ:各7.8mmφ×30cm 計90cm
・カラム温度:40℃
・流量:0.8ml/min
・注入量:100μl
・溶離液:テトラヒドロフラン
・検出器:示差屈折計(RI)
・標準試料:ポリスチレン <Measurement of weight average molecular weight of aromatic ring-containing (meth) acrylic polymer (A)>
The weight average molecular weight of the aromatic ring-containing (meth) acrylic polymer (A) was measured by GPC (gel permeation chromatography).
・ Analyzer: manufactured by Tosoh Corporation, HLC-8120GPC
Column: manufactured by Tosoh Corporation, G7000H XL + GMH XL + GMH XL
・ Column size: 7.8mmφ × 30cm each 90cm in total
-Column temperature: 40 ° C
・ Flow rate: 0.8ml / min
・ Injection volume: 100 μl
・ Eluent: Tetrahydrofuran ・ Detector: Differential refractometer (RI)
Standard sample: polystyrene
厚さ80μmのポリビニルアルコールフィルムを、速度比の異なるロール間において、30℃、0.3%濃度のヨウ素溶液中で1分間染色しながら、3倍まで延伸した。その後、60℃、4%濃度のホウ酸、10%濃度のヨウ化カリウムを含む水溶液中に0.5分間浸漬しながら総合延伸倍率が6倍になるように延伸した。次いで、30℃、1.5%濃度のヨウ化カリウムを含む水溶液中に10秒間浸漬することで洗浄した後、50℃で4分間乾燥を行い、厚さ20μmの偏光子を得た。当該偏光子の両面に、けん化処理した厚さ40μmのトリアセチルセルロースフィルムを、それぞれ、ポリビニルアルコール系接着剤により貼り合せて偏光フィルムを作成した。以下、これをTAC系偏光フィルム(1)という。 <Creation of polarizing film (1)>
A 80 μm-thick polyvinyl alcohol film was stretched up to 3 times between rolls with different speed ratios while being dyed in an iodine solution of 0.3% concentration at 30 ° C. for 1 minute. Thereafter, the film was stretched so that the total stretch ratio was 6 times while being immersed in an aqueous solution containing 60% at 4% concentration of boric acid and 10% concentration of potassium iodide for 0.5 minutes. Next, after washing by immersing in an aqueous solution containing potassium iodide at 30 ° C. and 1.5% concentration for 10 seconds, drying was performed at 50 ° C. for 4 minutes to obtain a polarizer having a thickness of 20 μm. A saponified 40 μm thick triacetyl cellulose film was bonded to both surfaces of the polarizer with a polyvinyl alcohol-based adhesive, respectively, to prepare polarizing films. Hereinafter, this is referred to as a TAC polarizing film (1).
薄型偏光膜を作製するため、まず、非晶性PET基材に9μm厚のPVA層が製膜された積層体を延伸温度130℃の空中補助延伸によって延伸積層体を生成し、次に、延伸積層体を染色によって着色積層体を生成し、さらに着色積層体を延伸温度65度のホウ酸水中延伸によって総延伸倍率が5.94倍になるように非晶性PET基材と一体に延伸された4μm厚のPVA層を含む光学フィルム積層体を生成した。このような2段延伸によって非晶性PET基材に製膜されたPVA層のPVA分子が高次に配向され、染色によって吸着されたヨウ素がポリヨウ素イオン錯体として一方向に高次に配向された高機能偏光膜を構成する、厚さ4μmのPVA層を含む光学フィルム積層体を生成することができた。更に、当該光学フィルム積層体の偏光膜の表面にポリビニルアルコール系接着剤を塗布しながら、けん化処理した40μm厚のアクリル樹脂フィルムを貼合せたのち、非晶性PET基材を剥離し、薄型偏光膜を用いた偏光フィルムを作製した。以下、これを薄型偏光フィルム(2)という。 <Creation of polarizing film (2)>
In order to produce a thin polarizing film, first, a laminated body in which a PVA layer having a thickness of 9 μm is formed on an amorphous PET substrate is produced by air-assisted stretching at a stretching temperature of 130 ° C., and then stretched. A colored laminate is produced by dyeing the laminate, and the colored laminate is further stretched integrally with an amorphous PET substrate so that the total draw ratio is 5.94 times by stretching in boric acid water at a stretching temperature of 65 degrees. An optical film laminate including a 4 μm thick PVA layer was produced. The PVA molecules in the PVA layer formed on the amorphous PET substrate by such two-stage stretching are oriented in the higher order, and the iodine adsorbed by the dyeing is oriented in the one direction as the polyiodine ion complex. It was possible to produce an optical film laminate including a PVA layer having a thickness of 4 μm and constituting a highly functional polarizing film. Further, after applying a saponified 40 μm thick acrylic resin film while applying a polyvinyl alcohol adhesive on the surface of the polarizing film of the optical film laminate, the amorphous PET substrate was peeled off, A polarizing film using the film was prepared. Hereinafter, this is referred to as a thin polarizing film (2).
薄型偏光膜を作製するため、まず、非晶性PET基材に9μm厚のPVA層が製膜された積層体を延伸温度130℃の空中補助延伸によって延伸積層体を生成し、次に、延伸積層体を染色によって着色積層体を生成し、さらに着色積層体を延伸温度65度のホウ酸水中延伸によって総延伸倍率が5.94倍になるように非晶性PET基材と一体に延伸された4μm厚のPVA層を含む光学フィルム積層体を生成した。このような2段延伸によって非晶性PET基材に製膜されたPVA層のPVA分子が高次に配向され、染色によって吸着されたヨウ素がポリヨウ素イオン錯体として一方向に高次に配向された高機能偏光膜を構成する、厚さ4μmのPVA層を含む光学フィルム積層体を生成することができた。更に、当該光学フィルム積層体の偏光膜の表面にポリビニルアルコール系接着剤を塗布しながら、けん化処理した40μm厚のトリアセチルセルロースフィルムを貼合せたのち、非晶性PET基材を剥離した後、他の片面に厚さ33μmのノルボルネン系フィルムを、それぞれ、ポリビニルアルコール系接着剤により貼り合せて、薄型偏光膜を用いた偏光フィルムを作製した。以下、これを薄型偏光フィルム(3)という。 <Creation of polarizing film (3)>
In order to produce a thin polarizing film, first, a laminated body in which a PVA layer having a thickness of 9 μm is formed on an amorphous PET substrate is produced by air-assisted stretching at a stretching temperature of 130 ° C., and then stretched. A colored laminate is produced by dyeing the laminate, and the colored laminate is further stretched integrally with an amorphous PET substrate so that the total draw ratio is 5.94 times by stretching in boric acid water at a stretching temperature of 65 degrees. An optical film laminate including a 4 μm thick PVA layer was produced. The PVA molecules in the PVA layer formed on the amorphous PET substrate by such two-stage stretching are oriented in the higher order, and the iodine adsorbed by the dyeing is oriented in the one direction as the polyiodine ion complex. It was possible to produce an optical film laminate including a PVA layer having a thickness of 4 μm and constituting a highly functional polarizing film. Furthermore, after applying the polyvinyl alcohol adhesive to the surface of the polarizing film of the optical film laminate, after laminating the saponified 40 μm thick triacetyl cellulose film, after peeling the amorphous PET substrate, A norbornene-based film having a thickness of 33 μm was bonded to the other surface with a polyvinyl alcohol-based adhesive, thereby producing a polarizing film using a thin polarizing film. Hereinafter, this is referred to as a thin polarizing film (3).
<芳香族環含有(メタ)アクリル系ポリマー(A-1)の調製>
冷却管、窒素導入管、温度計及び撹拌装置を備えた反応容器に、アクリル酸ブチル90部、ベンジルアクリレート(BzA)5部、アクリル酸4-ヒドロキシブチル5部、及び開始剤として、AIBNをモノマー(固形分)100部に対して1部を酢酸エチルと共に加えて窒素ガス気流下、60℃で7時間反応させた後、その反応液に酢酸エチルを加えて、重量平均分子量120万の芳香族環含有(メタ)アクリル系ポリマー(A-1)を含有する溶液を得た(固形分濃度30重量%)。 Production Example 1
<Preparation of aromatic ring-containing (meth) acrylic polymer (A-1)>
In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirring device, 90 parts of butyl acrylate, 5 parts of benzyl acrylate (BzA), 5 parts of 4-hydroxybutyl acrylate, and AIBN as a monomer (Solid content) 1 part per 100 parts is added with ethyl acetate and reacted at 60 ° C. for 7 hours under a nitrogen gas stream. Then, ethyl acetate is added to the reaction solution to give an aromatic having a weight average molecular weight of 1,200,000. A solution containing the ring-containing (meth) acrylic polymer (A-1) was obtained (solid content concentration 30% by weight).
<芳香族環含有(メタ)アクリル系ポリマー(A-2)の調製>
製造例1において、モノマー混合物として、アクリル酸ブチル87部、ベンジルアクリレート10部、アクリル酸4-ヒドロキシブチル3部を含有するモノマー混合物を用いたこと以外は、製造例1と同様にして、重量平均分子量130万の芳香族環含有(メタ)アクリル系ポリマー(A-2)の溶液を調製した。 Production Example 2
<Preparation of aromatic ring-containing (meth) acrylic polymer (A-2)>
In Production Example 1, a weight average was obtained in the same manner as in Production Example 1 except that a monomer mixture containing 87 parts of butyl acrylate, 10 parts of benzyl acrylate, and 3 parts of 4-hydroxybutyl acrylate was used as the monomer mixture. A solution of an aromatic ring-containing (meth) acrylic polymer (A-2) having a molecular weight of 1.3 million was prepared.
<芳香族環含有(メタ)アクリル系ポリマー(A-3)の調製>
製造例1において、モノマー混合物として、アクリル酸ブチル82部、ベンジルアクリレート15部、アクリル酸4-ヒドロキシブチル3部を含有するモノマー混合物を用いたこと以外は、製造例1と同様にして、重量平均分子量130万の芳香族環含有(メタ)アクリル系ポリマー(A-3)の溶液を調製した。 Production Example 3
<Preparation of aromatic ring-containing (meth) acrylic polymer (A-3)>
In Production Example 1, a weight average was obtained in the same manner as in Production Example 1 except that a monomer mixture containing 82 parts of butyl acrylate, 15 parts of benzyl acrylate, and 3 parts of 4-hydroxybutyl acrylate was used as the monomer mixture. A solution of an aromatic ring-containing (meth) acrylic polymer (A-3) having a molecular weight of 1.3 million was prepared.
<芳香族環含有(メタ)アクリル系ポリマー(A-4)の調製>
製造例1において、モノマー混合物として、アクリル酸ブチル77部、ベンジルアクリレート20部、アクリル酸4-ヒドロキシブチル3部を含有するモノマー混合物を用いたこと以外は、製造例1と同様にして、重量平均分子量135万の芳香族環含有(メタ)アクリル系ポリマー(A-4)の溶液を調製した。 Production Example 4
<Preparation of aromatic ring-containing (meth) acrylic polymer (A-4)>
In Production Example 1, the same as in Production Example 1, except that a monomer mixture containing 77 parts of butyl acrylate, 20 parts of benzyl acrylate, and 3 parts of 4-hydroxybutyl acrylate was used as the monomer mixture. A solution of an aromatic ring-containing (meth) acrylic polymer (A-4) having a molecular weight of 1.35 million was prepared.
<芳香族環含有(メタ)アクリル系ポリマー(A-5)の調製>
製造例1において、モノマー混合物として、アクリル酸ブチル72部、ベンジルアクリレート25部、アクリル酸4-ヒドロキシブチル3部を含有するモノマー混合物を用いたこと以外は、製造例1と同様にして、重量平均分子量120万の芳香族環含有(メタ)アクリル系ポリマー(A-5)の溶液を調製した。 Production Example 5
<Preparation of aromatic ring-containing (meth) acrylic polymer (A-5)>
In Production Example 1, a weight average was obtained in the same manner as in Production Example 1 except that a monomer mixture containing 72 parts of butyl acrylate, 25 parts of benzyl acrylate, and 3 parts of 4-hydroxybutyl acrylate was used as the monomer mixture. A solution of an aromatic ring-containing (meth) acrylic polymer (A-5) having a molecular weight of 1,200,000 was prepared.
<芳香族環含有(メタ)アクリル系ポリマー(A-6)の調製>
製造例1において、モノマー混合物として、アクリル酸ブチル67部、ベンジルアクリレート30部、アクリル酸4-ヒドロキシブチル3部を含有するモノマー混合物を用いたこと以外は、製造例1と同様にして、重量平均分子量120万の芳香族環含有(メタ)アクリル系ポリマー(A-6)の溶液を調製した。 Production Example 6
<Preparation of aromatic ring-containing (meth) acrylic polymer (A-6)>
In Production Example 1, a weight average was obtained in the same manner as in Production Example 1 except that a monomer mixture containing 67 parts of butyl acrylate, 30 parts of benzyl acrylate, and 3 parts of 4-hydroxybutyl acrylate was used as the monomer mixture. A solution of an aromatic ring-containing (meth) acrylic polymer (A-6) having a molecular weight of 1,200,000 was prepared.
<芳香族環含有(メタ)アクリル系ポリマー(A-7)の調製>
製造例1において、モノマー混合物として、アクリル酸ブチル82部、フェノキシエチルアクリレート(PEA)15部、アクリル酸4-ヒドロキシブチル3部を含有するモノマー混合物を用いたこと以外は、製造例1と同様にして、重量平均分子量130万の芳香族環含有(メタ)アクリル系ポリマー(A-7)の溶液を調製した。 Production Example 7
<Preparation of aromatic ring-containing (meth) acrylic polymer (A-7)>
In Production Example 1, the same procedure as in Production Example 1 was used, except that a monomer mixture containing 82 parts of butyl acrylate, 15 parts of phenoxyethyl acrylate (PEA), and 3 parts of 4-hydroxybutyl acrylate was used. Then, a solution of an aromatic ring-containing (meth) acrylic polymer (A-7) having a weight average molecular weight of 1.3 million was prepared.
<芳香族環含有(メタ)アクリル系ポリマー(A-8)の調製>
製造例1において、モノマー混合物として、アクリル酸ブチル77部、フェノキシエチルアクリレート20部、アクリル酸4-ヒドロキシブチル3部を含有するモノマー混合物を用いたこと以外は、製造例1と同様にして、重量平均分子量125万の芳香族環含有(メタ)アクリル系ポリマー(A-8)の溶液を調製した。 Production Example 8
<Preparation of aromatic ring-containing (meth) acrylic polymer (A-8)>
In Production Example 1, the same weight as in Production Example 1 was used, except that a monomer mixture containing 77 parts of butyl acrylate, 20 parts of phenoxyethyl acrylate, and 3 parts of 4-hydroxybutyl acrylate was used as the monomer mixture. A solution of an aromatic ring-containing (meth) acrylic polymer (A-8) having an average molecular weight of 1.25 million was prepared.
<芳香族環を含有しない(メタ)アクリル系ポリマー(A-9)の調製>
製造例1において、モノマー混合物として、アクリル酸ブチル97部、アクリル酸4-ヒドロキシブチル3部を含有するモノマー混合物を用いたこと以外は、製造例1と同様にして、重量平均分子量135万であって、芳香族環を含有しない(メタ)アクリル系ポリマー(A-9)の溶液を調製した。 Production Example 9
<Preparation of (meth) acrylic polymer (A-9) containing no aromatic ring>
In Preparation Example 1, the weight average molecular weight was 1.35 million as in Preparation Example 1, except that a monomer mixture containing 97 parts of butyl acrylate and 3 parts of 4-hydroxybutyl acrylate was used as the monomer mixture. Then, a solution of (meth) acrylic polymer (A-9) containing no aromatic ring was prepared.
(粘着剤組成物の調製)
製造例1で得られた芳香族環含有(メタ)アクリル系ポリマー(A-1)溶液の固形分100部あたり0.1部のトリメチロールプロパンキシリレンジイソシアネート(三井化学(株)製:タケネートD110N)と、ジベンゾイルパーオキサイド0.3部と、0.1部のγ-グリシドキシプロピルメトキシシラン(信越化学工業(株)製:KBM-403)と、ビス(ノナフルオロブタンスルホニル)イミドリチウム(商品名「EF-N445」、三菱マテリアル電子化成社製)1部を配合して、アクリル系粘着剤溶液を得た。 Example 1
(Preparation of adhesive composition)
0.1 part of trimethylolpropan xylylene diisocyanate (manufactured by Mitsui Chemicals, Inc .: Takenate D110N per 100 parts of solid content of the aromatic ring-containing (meth) acrylic polymer (A-1) solution obtained in Production Example 1 ), 0.3 part of dibenzoyl peroxide, 0.1 part of γ-glycidoxypropylmethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-403), and bis (nonafluorobutanesulfonyl) imide lithium 1 part (trade name “EF-N445”, manufactured by Mitsubishi Materials Electronic Chemical Co., Ltd.) was blended to obtain an acrylic pressure-sensitive adhesive solution.
前記粘着剤溶液をシリコーン系剥離剤で処理されたポリエチレンテレフタレートフィルム(基材)の表面に、ファウンテンコータで均一に塗工し、155℃の空気循環式恒温オーブンで2分間乾燥し、基材の表面に厚さ20μmの粘着剤層を形成した。次いで、TAC系偏光フィルム(1)に、粘着剤層を形成したセパレータを移着させ、粘着剤層付光学フィルムを作製した。 (Preparation of optical film with adhesive layer)
The pressure-sensitive adhesive solution is uniformly coated on the surface of a polyethylene terephthalate film (base material) treated with a silicone-based release agent with a fountain coater, dried in an air circulation type thermostatic oven at 155 ° C. for 2 minutes, A pressure-sensitive adhesive layer having a thickness of 20 μm was formed on the surface. Subsequently, the separator which formed the adhesive layer was transferred to the TAC polarizing film (1), and the optical film with an adhesive layer was produced.
実施例1において、粘着剤組成物の調製にあたり、各成分の使用量を表1および表2に示すように変えたこと、あるいは偏光フィルムの種類を変更したこと以外は、実施例1と同様にして、粘着剤層付偏光フィルムを作製した。 Examples 2-32 and Comparative Examples 1-4
In Example 1, preparation of the pressure-sensitive adhesive composition was carried out in the same manner as in Example 1 except that the amount of each component used was changed as shown in Tables 1 and 2 or the type of polarizing film was changed. Thus, a polarizing film with an adhesive layer was produced.
粘着剤層付偏光フィルムのセパレータフィルムを剥がした後、粘着剤表面の表面抵抗値(Ω/□)を三菱化学アナリテック社製MCP-HT450を用いて測定した。 <Surface resistance value: Initial resistance value>
After removing the separator film of the polarizing film with the pressure-sensitive adhesive layer, the surface resistance value (Ω / □) of the pressure-sensitive adhesive surface was measured using MCP-HT450 manufactured by Mitsubishi Chemical Analytech.
作製された粘着剤層付偏光フィルムを100mm×100mmの大きさに切断し、液晶パネルに貼り付けた。このパネルを10000cdの輝度を持つバックライト上に置き、静電気発生装置であるESD(SANKI社製,ESD-8012A)を用いて5kvの静電気を発生させることで液晶の配向乱れを起こした。その配向不良による表示不良の回復時間(秒)を、瞬間マルチ測光検出器(大塚電子社製,MCPD-3000)を用いて測定し、下記基準で評価した。
◎:表示不良が1秒未満で消失した。
○:表示不良が1秒以上10秒未満で消失した。
×:表示不良が10秒以上で消失した。 <Evaluation of static electricity unevenness>
The produced polarizing film with an adhesive layer was cut into a size of 100 mm × 100 mm and attached to a liquid crystal panel. This panel was placed on a backlight having a luminance of 10000 cd, and 5 kv of static electricity was generated by using ESD (SANKI, ESD-8012A) which is a static electricity generator, thereby causing alignment disorder of the liquid crystal. The display failure recovery time (seconds) due to the alignment failure was measured using an instantaneous multiphotometric detector (manufactured by Otsuka Electronics Co., Ltd., MCPD-3000) and evaluated according to the following criteria.
A: Display failure disappeared in less than 1 second.
○: Display failure disappeared in 1 second or more and less than 10 seconds.
X: Display defect disappeared in 10 seconds or more.
実施例、比較例で得られた粘着剤層付偏光フィルムを60℃/95%RHの恒温恒湿機に投入し、48時間後取り出したのち、60℃で2時間乾燥したのちセパレータフィルムを剥がし、粘着剤表面の表面抵抗値を(株)三菱化学アナリテック製MCP-HT450を用いて測定した。 <Surface resistance value: resistance value after humidification test>
The polarizing film with the pressure-sensitive adhesive layer obtained in Examples and Comparative Examples was put into a constant temperature and humidity chamber of 60 ° C./95% RH, taken out after 48 hours, dried at 60 ° C. for 2 hours, and then peeled off the separator film. The surface resistance value of the pressure-sensitive adhesive surface was measured using MCP-HT450 manufactured by Mitsubishi Chemical Analytech Co., Ltd.
実施例、比較例で得られた粘着剤層付偏光フィルムのセパレータフィルムを剥がし、無アルカリガラスに貼り合わせ、50℃、5atm、15分間のオートクレーブ処理を行った後、80℃の加熱オーブンおよび60℃/90%RHの恒温恒湿機に投入した。500h後の偏光フィルムの剥がれの有無を確認し、全く剥がれが認められなかったものを◎、目視では確認できない程度の剥がれを○、目視で確認できる小さな剥がれを△、明らかな剥がれが認められたものを×とした。 <Durability>
The separator film of the polarizing film with an adhesive layer obtained in Examples and Comparative Examples was peeled off and bonded to alkali-free glass, and after autoclaving at 50 ° C., 5 atm for 15 minutes, a heating oven at 80 ° C. and 60 ° C. It put into the constant temperature / humidity machine of ℃ / 90% RH. After confirming the presence or absence of peeling of the polarizing film after 500 hours, ◎ indicates that peeling was not observed at all, ○ indicates peeling that cannot be confirmed visually, Δ indicates small peeling that can be visually confirmed, and clear peeling was observed. The thing was made into x.
サンプルを、縦420mm×横320mmのサイズに切り出したものを2枚用意した。このサンプルを、厚さ0.07mmの無アルカリガラス板の両面にクロスニコルになるようにラミネーターにて貼り合せた。次いで、50℃、5atmで15分間のオートクレーブ処理を行って二次サンプルとした(初期)。次いで、二次サンプルを、85℃の条件下で100時間の処理を行った(加熱後)。初期および加熱後の二次サンプルを、1万カンデラのバックライト上に置き、光漏れを下記の基準により、目視で評価した。
◎:コーナームラの発生がなく、実用上問題ない。
○:コーナームラがわずかながら発生しているが、表示領域には表れていないので、実用上問題ない。
×:コーナームラが発生して表示領域にはきつく表れており、実用上問題がある。 <Corner unevenness>
Two samples prepared by cutting the sample into a size of 420 mm long × 320 mm wide were prepared. This sample was bonded by a laminator so as to be crossed Nicol on both surfaces of a non-alkali glass plate having a thickness of 0.07 mm. Subsequently, the autoclave process was performed for 15 minutes at 50 degreeC and 5 atm, and it was set as the secondary sample (initial stage). Next, the secondary sample was treated for 100 hours under the condition of 85 ° C. (after heating). The initial and heated secondary samples were placed on a 10,000 candela backlight, and light leakage was visually evaluated according to the following criteria.
A: There is no occurrence of corner unevenness and there is no practical problem.
○: Corner unevenness occurs slightly, but does not appear in the display area, so there is no practical problem.
X: Corner unevenness occurs and appears in the display area, which is problematic in practical use.
架橋剤(C)における、「C-1」は三井化学ポリウレタン社製のイソシアネート架橋剤(商品名「タケネートD110N」,トリメチロールプロパンキシリレンジイソシアネート)、「C-2」は日本油脂社製のジベンゾイルパーオキサイド(ナイパーBMT)を示す。
シランカップリング剤(D)における「D-1」は信越化学工業社製のKBM403を示す。
ポリエーテル化合物(E)における「E-1」は、(商品名「サイリルSAT10」、カネカ社製、「E-2」は、(商品名「SIB1824.82」、GELEST社製)を示す。 In Tables 1 and 2, “B-1” in the ionic compound (B) is bis (nonafluorobutanesulfonyl) imidolithium (trade name “EF-N445”, manufactured by Mitsubishi Materials Electronic Chemicals), “B -2 ”is bis (heptafluoropropanesulfonyl) imide lithium (manufactured by Wako Pure Chemical Industries, Ltd.), and“ B-3 ”is cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide lithium (trade name“ EF- ”). N305 ", manufactured by Mitsubishi Materials Electronic Chemical Co., Ltd.)," B-4 "is 1-butyl-3-methylpyridinium bis (nonafluorobutanesulfonyl) imide (trade name" BuMePy · N441 ", manufactured by Mitsubishi Materials Electronic Chemicals) , “B-5” is bis (trifluoromethanesulfonyl) imide lithium (manufactured by Wako Pure Chemical Industries, Ltd.), and “B-6” is 1-butyl -3-Methylpyridinium bis (trifluoromethanesulfonyl) imide (trade name “CIL-312”, manufactured by Nippon Carlit), “B-7” is 1,1,2,2,3,3-hexafluoropropane- 1,3-disulfonic acid dilithium salt (trade name “EF-3005”, manufactured by Mitsubishi Materials Electronic Chemical Co., Ltd.), “B-8” represents ethylmethylpyrrolidinium bis (trifluoromethanesulfonyl) imide.
In the cross-linking agent (C), “C-1” is an isocyanate cross-linking agent (trade name “Takenate D110N”, trimethylolpropane xylylene diisocyanate) manufactured by Mitsui Chemicals Polyurethanes, and “C-2” is a distillate manufactured by Nippon Oil & Fats Co., Ltd. Benzoyl peroxide (Nyper BMT) is shown.
“D-1” in the silane coupling agent (D) represents KBM403 manufactured by Shin-Etsu Chemical Co., Ltd.
In the polyether compound (E), “E-1” indicates (trade name “Syryl SAT10”, manufactured by Kaneka Corporation, and “E-2” indicates (trade name “SIB1824.82”, manufactured by GELEST).
Claims (23)
- (メタ)アクリル系ポリマー(A)、ならびにアニオン成分およびカチオン成分を有するイオン性化合物(B)を含有する粘着剤組成物であって、
前記(メタ)アクリル系ポリマー(A)が、モノマー単位として、芳香族環含有アルキル(メタ)アクリレートを含有する芳香族環含有(メタ)アクリル系ポリマー(A)であることを特徴とする粘着剤組成物。 A pressure-sensitive adhesive composition containing a (meth) acrylic polymer (A) and an ionic compound (B) having an anionic component and a cationic component,
The pressure-sensitive adhesive, wherein the (meth) acrylic polymer (A) is an aromatic ring-containing (meth) acrylic polymer (A) containing an aromatic ring-containing alkyl (meth) acrylate as a monomer unit. Composition. - 前記アニオン成分が、有機基を有し、かつ炭素数が2以上であるアニオン成分である請求項1に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 1, wherein the anion component is an anion component having an organic group and having 2 or more carbon atoms.
- 前記アニオン成分が、下記一般式(1):
(CnF2n+1SO2)2N- (1)
(一般式(1)中、nは1~10の整数)、下記一般式(2):
CF2(CmF2mSO2)2N- (2)
(一般式(2)中、mは2~10の整数):および下記一般式(3):
-O3S(CF2)l SO3 - (3)
(一般式(3)中、lは3~10の整数)で表される少なくとも1種のアニオン成分である請求項1または2に記載の粘着剤組成物。 The anion component is represented by the following general formula (1):
(C n F 2n + 1 SO 2 ) 2 N − (1)
(In the general formula (1), n is an integer of 1 to 10), the following general formula (2):
CF 2 (C m F 2m SO 2 ) 2 N − (2)
(In the general formula (2), m is an integer of 2 to 10): and the following general formula (3):
- O 3 S (CF 2) l SO 3 - (3)
The pressure-sensitive adhesive composition according to claim 1 or 2, which is at least one anion component represented by (wherein l is an integer of 3 to 10 in the general formula (3)). - 前記イオン性化合物(B)が有するカチオン成分が、アルカリ金属カチオンおよび有機カチオンの少なくとも1種である請求項1~3のいずれかに記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 1 to 3, wherein the cation component of the ionic compound (B) is at least one of an alkali metal cation and an organic cation.
- 前記イオン性化合物(B)が有するカチオン成分が、リチウムカチオンである請求項1~4のいずれかに記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 1 to 4, wherein the cation component of the ionic compound (B) is a lithium cation.
- 前記イオン性化合物(B)が有するカチオン成分が、炭素数4~10の有機カチオンである請求項1~5のいずれかに記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 1 to 5, wherein the cation component of the ionic compound (B) is an organic cation having 4 to 10 carbon atoms.
- 前記イオン性化合物(B)が有するアニオン成分が、ビス(トリフルオロメタンスルホニル)イミドアニオン、ビス(ヘプタフルオロプロパンスルホニル)イミドアニオン、ビス(ノナフルオロブタンスルホニル)イミドアニオン、シクロ-ヘキサフルオロプロパン-1,3-ビス(スルホニル)イミドアニオン、およびヘキサフルオロプロパン-1,3-ジスルホン酸アニオンの少なくとも1種である請求項1~6のいずれかに記載の粘着剤組成物。 The anionic component of the ionic compound (B) is bis (trifluoromethanesulfonyl) imide anion, bis (heptafluoropropanesulfonyl) imide anion, bis (nonafluorobutanesulfonyl) imide anion, cyclo-hexafluoropropane-1, The pressure-sensitive adhesive composition according to any one of claims 1 to 6, which is at least one of a 3-bis (sulfonyl) imide anion and a hexafluoropropane-1,3-disulfonic acid anion.
- 前記芳香族環含有(メタ)アクリル系ポリマー(A)100重量部に対して、前記イオン性化合物(B)を0.001~10重量部含有する請求項1~7のいずれかに記載の粘着剤組成物。 The pressure-sensitive adhesive according to any one of claims 1 to 7, comprising 0.001 to 10 parts by weight of the ionic compound (B) with respect to 100 parts by weight of the aromatic ring-containing (meth) acrylic polymer (A). Agent composition.
- 前記芳香族環含有アルキル(メタ)アクリレートとして、ベンジル(メタ)アクリレートおよびフェノキシエチル(メタ)アクリレートの少なくとも1種を含有する請求項1~8のいずれかに記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 1 to 8, which contains at least one of benzyl (meth) acrylate and phenoxyethyl (meth) acrylate as the aromatic ring-containing alkyl (meth) acrylate.
- 芳香族環含有(メタ)アクリル系ポリマー(A)が、モノマー単位として、さらにヒドロキシル基含有モノマーを含有する請求項1~9のいずれかに記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 1 to 9, wherein the aromatic ring-containing (meth) acrylic polymer (A) further contains a hydroxyl group-containing monomer as a monomer unit.
- 芳香族環含有(メタ)アクリル系ポリマー(A)が、モノマー単位として、さらにカルボキシル基含有モノマーを含有する請求項1~10のいずれかに記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 1 to 10, wherein the aromatic ring-containing (meth) acrylic polymer (A) further contains a carboxyl group-containing monomer as a monomer unit.
- さらに、架橋剤(C)を含有する請求項1~11のいずれかに記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 1 to 11, further comprising a crosslinking agent (C).
- 前記芳香族環含有(メタ)アクリル系ポリマー(A)100重量部に対して、前記架橋剤(C)を0.01~20重量部含有する請求項12に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 12, comprising 0.01 to 20 parts by weight of the crosslinking agent (C) with respect to 100 parts by weight of the aromatic ring-containing (meth) acrylic polymer (A).
- 前記架橋剤(C)が、イソシアネート系化合物および過酸化物の少なくとも1種である請求項12または13に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 12 or 13, wherein the crosslinking agent (C) is at least one of an isocyanate compound and a peroxide.
- 前記芳香族環含有(メタ)アクリル系ポリマー(A)100重量部に対して、さらに、シランカップリング剤(D)を0.001~5重量部含有する請求項1~14のいずれかに記載の粘着剤組成物。 The silane coupling agent (D) is further contained in an amount of 0.001 to 5 parts by weight with respect to 100 parts by weight of the aromatic ring-containing (meth) acrylic polymer (A). Adhesive composition.
- 前記芳香族環含有(メタ)アクリル系ポリマー(A)100重量部に対して、さらにポリエーテル変性シリコーン(E)を0.001~10重量部含有する請求項1~15のいずれかに記載の粘着剤組成物。 The polyether-modified silicone (E) is further contained in an amount of 0.001 to 10 parts by weight per 100 parts by weight of the aromatic ring-containing (meth) acrylic polymer (A). Adhesive composition.
- 前記芳香族環含有(メタ)アクリル系ポリマー(A)の重量平均分子量が、50万~300万である請求項1~16のいずれかに記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 1 to 16, wherein the aromatic ring-containing (meth) acrylic polymer (A) has a weight average molecular weight of 500,000 to 3,000,000.
- 請求項1~17のいずれかに記載の粘着剤組成物から形成されたものであることを特徴とする粘着剤層。 A pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to any one of claims 1 to 17.
- 偏光子の片面または両面に透明保護フィルムを有する偏光フィルムと、請求項18に記載の粘着剤層とを少なくとも有する粘着剤層付偏光フィルム。 The polarizing film with an adhesive layer which has at least the polarizing film which has a transparent protective film on the single side | surface or both surfaces of a polarizer, and the adhesive layer of Claim 18.
- 前記透明保護フィルムがトリアセチルセルロースフィルム、(メタ)アクリル樹脂フィルム、または環状ポリオレフィンポリマーフィルムである請求項19記載の粘着剤層付偏光フィルム。 The polarizing film with an adhesive layer according to claim 19, wherein the transparent protective film is a triacetyl cellulose film, a (meth) acrylic resin film, or a cyclic polyolefin polymer film.
- 前記偏光子の厚みが1~10μmである請求項19または20に記載の粘着剤層付偏光フィルム。 The polarizing film with an adhesive layer according to claim 19 or 20, wherein the polarizer has a thickness of 1 to 10 µm.
- 前記偏光フィルムと前記粘着剤層との間に、易接着層を有する請求項19~21のいずれかに記載の粘着剤層付偏光フィルム。 The polarizing film with a pressure-sensitive adhesive layer according to any one of claims 19 to 21, further comprising an easy-adhesion layer between the polarizing film and the pressure-sensitive adhesive layer.
- 請求項19~22のいずれかに記載の粘着剤層付偏光フィルムを少なくとも1つ用いたことを特徴とする画像表示装置。 An image display device using at least one polarizing film with an adhesive layer according to any one of claims 19 to 22.
Priority Applications (3)
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CN201280054708.4A CN103930510B (en) | 2011-11-24 | 2012-11-16 | Adhesive composition, adhesive phase, the polarizing coating of band adhesive phase and image processing system |
KR1020147002870A KR102152585B1 (en) | 2011-11-24 | 2012-11-16 | Adhesive composition, adhesive layer, polarizing film having adhesive layer, and image formation device |
US14/360,550 US20140322457A1 (en) | 2011-11-24 | 2012-11-16 | Adhesive composition, adhesive layer, polarizing film having adhesive agent layer, and image forming device |
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JP2011-256440 | 2011-11-24 | ||
JP2011256440 | 2011-11-24 | ||
JP2012-251239 | 2012-11-15 | ||
JP2012251239A JP6195707B2 (en) | 2011-11-24 | 2012-11-15 | Adhesive composition, adhesive layer, polarizing film with adhesive layer, and image forming apparatus |
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WO2013077271A1 true WO2013077271A1 (en) | 2013-05-30 |
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PCT/JP2012/079819 WO2013077271A1 (en) | 2011-11-24 | 2012-11-16 | Adhesive composition, adhesive layer, polarizing film having adhesive layer, and image formation device |
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US (1) | US20140322457A1 (en) |
JP (1) | JP6195707B2 (en) |
KR (1) | KR102152585B1 (en) |
CN (2) | CN103930510B (en) |
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KR20140094499A (en) | 2014-07-30 |
TWI579356B (en) | 2017-04-21 |
CN107022328A (en) | 2017-08-08 |
TW201730313A (en) | 2017-09-01 |
CN103930510B (en) | 2016-11-23 |
JP2013129822A (en) | 2013-07-04 |
KR102152585B1 (en) | 2020-09-07 |
CN103930510A (en) | 2014-07-16 |
US20140322457A1 (en) | 2014-10-30 |
JP6195707B2 (en) | 2017-09-13 |
TW201333136A (en) | 2013-08-16 |
TWI606106B (en) | 2017-11-21 |
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